U.S. patent application number 14/510543 was filed with the patent office on 2015-04-02 for efficient, manganese catalyzed process to decompose cyanide ions and hydrogen cyanide for water decontamination.
The applicant listed for this patent is The Trustees of Princeton University. Invention is credited to John T. Groves.
Application Number | 20150090672 14/510543 |
Document ID | / |
Family ID | 52739051 |
Filed Date | 2015-04-02 |
United States Patent
Application |
20150090672 |
Kind Code |
A1 |
Groves; John T. |
April 2, 2015 |
EFFICIENT, MANGANESE CATALYZED PROCESS TO DECOMPOSE CYANIDE IONS
AND HYDROGEN CYANIDE FOR WATER DECONTAMINATION
Abstract
Methods, kits, cartridges and compounds related to generating
chlorine dioxide by exposing ClO.sub.2.sup.- to at least one of a
manganese porphyrin catalyst or a manganese porphyrazine catalyst
are described. Methods, kits, cartridges and compounds related to
decomposed cyanide ions and hydrogen cyanide for water
decontamination.
Inventors: |
Groves; John T.; (Princeton,
NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Trustees of Princeton University |
Princeton |
PA |
US |
|
|
Family ID: |
52739051 |
Appl. No.: |
14/510543 |
Filed: |
October 9, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13818575 |
May 3, 2013 |
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PCT/US11/48396 |
Aug 19, 2011 |
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14510543 |
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61888689 |
Oct 9, 2013 |
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61376052 |
Aug 23, 2010 |
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61504460 |
Jul 5, 2011 |
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Current U.S.
Class: |
210/754 ;
252/176; 252/181; 540/140; 540/145 |
Current CPC
Class: |
B01J 31/1815 20130101;
C02F 1/725 20130101; B01J 2531/025 20130101; B01J 2531/72 20130101;
B01J 2231/70 20130101; C02F 2305/023 20130101; C02F 2101/18
20130101; C02F 1/76 20130101 |
Class at
Publication: |
210/754 ;
540/145; 540/140; 252/181; 252/176 |
International
Class: |
C02F 1/76 20060101
C02F001/76; B01J 31/22 20060101 B01J031/22 |
Goverment Interests
[0002] This invention was made with government support under Grant
#CHE-0616633 awarded by the National Science Foundation. The
government has certain rights in this invention.
Claims
1. A method of treating cyanide containing material comprising
exposing the cyanide containing material to ClO.sub.2.sup.- and at
least one catalyst selected from the group consisting of a
manganese porphyrin catalyst or a manganese porphyrazine
catalyst.
2. The method of claim 1, wherein the at least one catalyst
includes a manganese porphyrin catalyst having a structure of
formula I: ##STR00018## wherein the a is the oxidation state II,
III or IV of the Mn and R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
independently selected from the group consisting of TM2PyP, TM4PyP,
TDMImP, and TDMBImp, which have a structure of formulas II, III, IV
and V, respectively: ##STR00019## and at least one of R.sub.5,
R.sub.6, R.sub.7, R.sub.8, R.sub.9, and R.sub.10 are independently
selected from the group consisting of H; methyl; ethyl; propyl;
isopropyl; n-butyl; sec-butyl; isobutyl;
CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where n1=5-20;
CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2).sub.nAr--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; or
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p-- where Ar is
substituted or unsubstituted phenyl, substituted or unsubstituted
biphenyl, or substituted or unsubstituted naphthyl and when Ar is
the phenyl in --CH.sub.2--Ar--X, (CH.sub.2).sub.mAr--X, or
(CH.sub.2).sub.mAr--Y, the X or Y is attached ortho-meta- or para
to the --CH.sub.2-- attached to pyridoporphyrazine; n is 1 to 10; m
is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl.sub.1), CONH.sub.2,
CONH(alkyl.sub.1), CON(alkyl.sub.1).sub.2,
CO(CH.sub.2).sub.palkyl.sub.1, OPO.sub.3H.sub.2, PO.sub.3H.sub.2,
SO.sub.3H, NH.sub.2, N(alkyl.sub.1).sub.2, or
N(alkyl.sub.1).sub.3.sup.+, where alkyl.sub.1 is methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, or octyl; and L.sub.1 and
L.sub.2 are, independently absent, halide, oxo, aquo, hydroxo, CN,
OPO.sub.3H, or alcohol.
3. The method of claim 2, wherein R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are TDMBImp.
4. The method of claim 2, wherein R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are TM2PyP or R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are
TM4PyP.
5. The method of claim 1, wherein the at least one catalyst
includes a manganese porphyrazine catalyst having a structure of
formula VI: ##STR00020## wherein a is the oxidation state II, III
or IV of the Mn and each of A.sub.1, A.sub.2, A.sub.3, A.sub.4,
B.sub.1, B.sub.2, B.sub.3, B.sub.4, C.sub.1, C.sub.2, C.sub.3,
C.sub.4, D.sub.1, D.sub.2, D.sub.3 and D.sub.4 are independently
selected from N.sup.+--R.sub.n, N, C--H, C--X, and C--R.sub.n; when
N.sup.+--R.sub.n is selected, only one in each set of A.sub.1,
B.sub.1, C.sub.1, and D.sub.1; A.sub.2, B.sub.2, C.sub.2, and
D.sub.2; A.sub.3, B.sub.3, C.sub.3, and D.sub.3; or A.sub.4,
B.sub.4, C.sub.4, and D.sub.4 is N.sup.+--R.sub.n; when N is
selected, only one in each set of A.sub.1, B.sub.1, C.sub.1, and
D.sub.1; A.sub.2, B.sub.2, C.sub.2, and D.sub.2; A.sub.3, B.sub.3,
C.sub.3, and D.sub.3; or A.sub.4, B.sub.4, C.sub.4, or D.sub.4 is
N; each R.sub.n is independently selected from the group consisting
of H; methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl;
isobutyl; CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where n1=5-20;
CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 and
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2).sub.nAr--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; o
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p--; and where Ar is
substituted or unsubstituted phenyl, substituted or unsubstituted
biphenyl, or substituted or unsubstituted naphthyl and when Ar is
the phenyl in --CH.sub.2--Ar--X, (CH.sub.2).sub.mAr--X, or
(CH.sub.2).sub.mAr--Y, the X or Y is attached ortho-meta- or para
to the --CH.sub.2-- attached to pyridoporphyrazine; n is 1 to 10; m
is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl.sub.1), CONH.sub.2,
CONH(alkyl.sub.1), CON(alkyl.sub.1).sub.2,
CO(CH.sub.2).sub.palkyl.sub.1, OPO.sub.3H.sub.2, PO.sub.3H.sub.2,
SO.sub.3H, NH.sub.2, N(alkyl.sub.1).sub.2, or
N(alkyl.sub.1).sub.3.sup.+, where alkyl.sub.1 is methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, or octyl; and L.sub.1 and
L.sub.2 are, independently absent, halide, oxo, aquo, hydroxo, CN,
OPO.sub.3H, or alcohol.
6. The method of claim 1, wherein the ClO.sub.2.sup.- is provided
from at least one substance selected from the group consisting of
chlorite salts.
7. The method of claim 1, wherein the ClO.sub.2.sup.- is provided
from at least one substance selected from the group consisting of
sodium chlorite, potassium chlorite, calcium chlorite and magnesium
chlorite.
8. The method of claim 1, wherein the ClO.sub.2.sup.- is mixed with
a solid filler.
9. The method of claim 1, wherein the ClO.sub.2.sup.- is adsorbed
on at least one substance selected from the group consisting of
clay, silica, alumina and organic polymers.
10. The method of claim 1, wherein at least one of the manganese
porphyrin catalyst or a manganese porphyrazine catalyst is adsorbed
on a solid support.
11. The method of claim 10, wherein the solid support includes a
substance selected from the group consisting of clay, silica,
alumina, glass beads, functionalized polystyrene or organic
polymers.
12. A kit for treating cyanide containing material comprising at
least one catalyst selected from the group consisting of a
manganese porphyrin catalyst or a manganese porphyrazine catalyst
and instructions to combine the at least one catalyst with
ClO.sub.2.sup.- in the presence of the cyanide containing
material.
13. The kit of claim 12, wherein the at least one catalyst includes
a manganese porphyrin catalyst having a structure of formula I:
##STR00021## wherein a is the oxidation state II, III or IV of the
Mn and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently
selected from the group consisting of TM2PyP, TM4PyP, TDMImP, and
TDMBImp, which have a structure of formulas II, III, IV and V,
respectively: ##STR00022## and at least one of R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, and R.sub.10 are independently selected
from the group consisting of H; methyl; ethyl; propyl; isopropyl;
n-butyl; sec-butyl; isobutyl; CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3
where n1=5-20; CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where
n2=0-20; --CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where
n3=0-20; --CH.sub.2--Ar--X; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.mAr--X; (CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y;
CH.sub.2CONH--Y; CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2).sub.nAr--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; or
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O,
(CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p-- where Ar is
substituted or unsubstituted phenyl, substituted or unsubstituted
biphenyl, or substituted or unsubstituted naphthyl and when Ar is
the phenyl in --CH.sub.2--Ar--X, (CH.sub.2).sub.mAr--X, or
(CH.sub.2).sub.mAr--Y, the X or Y is attached ortho-meta- or para
to the --CH.sub.2-- attached to pyridoporphyrazine; n is 1 to 10; m
is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl.sub.1), CONH.sub.2,
CONH(alkyl.sub.1), CON(alkyl.sub.1).sub.2,
CO(CH.sub.2).sub.palkyl.sub.1, OPO.sub.3H.sub.2, PO.sub.3H.sub.2,
SO.sub.3H, NH.sub.2, N(alkyl.sub.1).sub.2, or
N(alkyl.sub.1).sub.3.sup.+, where alkyl.sub.1 is methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, or octyl; and L.sub.1 and
L.sub.2 are, independently absent, halide, oxo, aquo, hydroxo, CN,
OPO.sub.3H, or alcohol.
14. The kit of claim 13, wherein R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are TDMBImp.
15. The kit of claim 13, wherein R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are TM2PyP or R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are
TM4PyP.
16. The kit of claim 12, wherein the at least one catalyst includes
a manganese porphyrazine catalyst having a structure of formula VI:
##STR00023## wherein a is the oxidation state II, III or IV of the
Mn and each of A.sub.1, A.sub.2, A.sub.3, A.sub.4, B.sub.1,
B.sub.2, B.sub.3, B.sub.4, C.sub.1, C.sub.2, C.sub.3, C.sub.4,
D.sub.1, D.sub.2, D.sub.3 and D.sub.4 are independently selected
from N.sup.+--R.sub.n, C--H, C--X, and C--R.sub.n; when
N.sup.+--R.sub.n is selected, only one in each set of A.sub.1,
B.sub.1, C.sub.1, and D.sub.1; A.sub.2, B.sub.2, C.sub.2, and
D.sub.2; A.sub.3, B.sub.3, C.sub.3, and D.sub.3; or A.sub.4,
B.sub.4, C.sub.4, and D.sub.4 is N.sup.+--R.sub.n; when N is
selected, only one in each set of A.sub.1, B.sub.1, C.sub.1, and
D.sub.1; A.sub.2, B.sub.2, C.sub.2, and D.sub.2; A.sub.3, B.sub.3,
C.sub.3, and D.sub.3; or A.sub.4, B.sub.4, C.sub.4, or D.sub.4 is
N; each R.sub.n is independently selected from the group consisting
of H; methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl;
isobutyl; CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where n1=5-20;
CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 and
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2).sub.nAr--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; o
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O,
(CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p--; and where Ar is
substituted or unsubstituted phenyl, substituted or unsubstituted
biphenyl, or substituted or unsubstituted naphthyl and when Ar is
the phenyl in --CH.sub.2--Ar--X, (CH.sub.2).sub.mAr--X, or
(CH.sub.2).sub.mAr--Y, the X or Y is attached ortho-meta- or para
to the --CH.sub.2-- attached to pyridoporphyrazine; n is 1 to 10; m
is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl.sub.1), CONH.sub.2,
CONH(alkyl.sub.1), CON(alkyl.sub.1).sub.2,
CO(CH.sub.2).sub.palkyl.sub.1, OPO.sub.3H.sub.2, PO.sub.3H.sub.2,
SO.sub.3H, NH.sub.2, N(alkyl.sub.1).sub.2, or
N(alkyl.sub.1).sub.3.sup.+, where alkyl.sub.1 is methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, or octyl; and L.sub.1 and
L.sub.2 are, independently absent, halide, oxo, aquo, hydroxo, CN,
OPO.sub.3H, or alcohol.
17. The kit of claim 12, wherein the ClO.sub.2.sup.- is provided
from at least one substance selected from the group consisting of
chlorite salts.
18. The kit of claim 12, wherein the ClO.sub.2.sup.- is provided
from at least one substance selected from the group consisting of
sodium chlorite, potassium chlorite, calcium chlorite and magnesium
chlorite.
19. The kit of claim 12, wherein the ClO.sub.2.sup.- is mixed with
a solid filler.
20. The kit of claim 12, wherein the ClO.sub.2.sup.- is adsorbed on
at least one substance selected from the group consisting of clay,
silica, alumina and organic polymers.
21. The kit of claim 12, wherein at least one of the manganese
porphyrin catalyst or a manganese porphyrazine catalyst is adsorbed
on a solid support.
22. The kit of claim 21, wherein the solid support includes a
substance selected from the group consisting of clay, silica,
alumina, glass beads, functionalized polystyrene or organic
polymers.
Description
[0001] This application claims the benefit of U.S. Provisional
Application No. 61/888,689, which was filed on Oct. 9, 2013 and is
incorporated herein by reference as if fully set forth. This
application is also a continuation-in-part of U.S. application Ser.
No. 13/818,575, which is a 35 U.S.C. .sctn.371 national stage of
PCT/US11/48396, which was filed Aug. 19, 2011 and claimed the
benefit of U.S. Provisional Application Nos. 61/376,052, filed Aug.
23, 2010, and 61/504,460, filed Jul. 5, 2011. All of the foregoing
are incorporated herein by reference as if fully set forth.
FIELD
[0003] The disclosure herein relates to oxidation of aqueous
cyanide.
BACKGROUND
[0004] Chlorine dioxide (ClO.sub.2) may be used in a variety of
settings. It is an oxidizing agent that is employed in place of
chlorine since it has superior antimicrobial properties and a
reduced tendency to produce harmful organic chlorine by-products.
Chlorine dioxide is used primarily (>95%) for bleaching of wood
pulp, but is also used for pathogen decontamination, water
treatment, bleaching of flour and disinfection of municipal
drinking water. Its most common use in water treatment is as a
pre-oxidant prior to chlorination of drinking water to destroy
natural water impurities that produce trihalomethanes on exposure
to free chlorine. Trihalomethanes are suspect carcinogenic
disinfection byproducts associated with chlorination of naturally
occurring organics in the raw water. Chlorine dioxide is also
superior to chlorine when operating above pH 7, in the presence of
ammonia and amines and/or for the control of biofilms in water
distribution systems. Chlorine dioxide is used in many industrial
water treatment applications, and as a biocide in cooling towers,
water processing and food processing. Chlorine dioxide is less
corrosive than chlorine and superior for the control of legionella
bacteria.
[0005] Chlorine dioxide is also more effective as a disinfectant
than chlorine in most circumstances against water borne pathogenic
microbes such as viruses, bacteria and protozoa--including cysts of
Giardia and the oocysts of Cryptosporidium.
[0006] Chlorine dioxide can also be used for air disinfection, and
was the principal agent used for decontamination of buildings in
the United States after the 2001 anthrax attacks. Recently, after
the disaster of Hurricane Katrina in New Orleans, La. and the
surrounding Gulf Coast, chlorine dioxide has been used to eradicate
dangerous mold from houses inundated by water from massive
flooding. Chlorine dioxide is used as an oxidant for phenol
destruction in waste water streams, control of zebra and quagga
mussels in water intakes and for odor control in the air scrubbers
of animal byproduct (rendering plants). Stablilized chlorine
dioxide can also be used in an oral rinse to treat oral disease and
malodor.
[0007] The industrial preparation of chlorine dioxide is
energy-intensive and fraught with health and safety issues.
Furthermore, due to the instability of ClO.sub.2 at high pressures,
the gas is often generated where it is to be used. Large-scale
production of ClO.sub.2 may involve the use of such reagents as
concentrated strong acids and/or externally-added oxidants (such as
Cl.sub.2, H.sub.2O.sub.2, or hypochlorite). Electrochemical methods
can directly oxidize ClO.sub.2.sup.- to ClO.sub.2 by a 1-electron
process but require considerable input of electrical energy and may
not be applicable in rural or underdeveloped areas of the world. An
iron-catalyzed decomposition of ClO.sub.2.sup.- has been shown to
afford ClO.sub.2 (in part), but only under very acidic conditions.
Since ClO.sub.2 is often generated where it is to be used, these
hazardous and/or costly methods must be implemented in facilities
that are primarily engineered for other purposes.
[0008] Cyanide ion (hydrogen cyanide and various cyanide salts) is
used in a variety of industrial processes such as mining operations
and chemical processing. It has found widespread use industrially,
especially for electro-plating, precious metals milling operations,
and coal processing. Because of potential health and environmental
hazards, there is a need to detoxify the cyanide-contaminated
effluents from these processes. Several cyanide treatment systems
have been developed, the most common of which is the
alkaline-chlorination-oxidation process. Oxidants for this process
include chlorine, hypochlorite, and chlorine dioxide, which oxidize
cyanide into cyanate and often ultimately into CO.sub.2. But still,
cyanide contamination of water and soils occurs commonly. There is
a clear need to decontaminate water or other materials that
contains cyanide ions or hydrogen cyanide.
SUMMARY
[0009] In an aspect, the invention relates to a method of
generating chlorine dioxide. The method includes exposing
ClO.sub.2.sup.- to at least one of a manganese porphyrin catalyst
or a manganese porphyrazine catalyst.
[0010] In an aspect, the invention relates to a kit for generating
chlorine dioxide. The kit includes at least one of a manganese
porphyrin catalyst or a manganese porphyrazine catalyst. The kit
also includes instructions to combine the at least one of a
manganese porphyrin catalyst or a manganese porphyrazine catalyst
with ClO.sub.2.sup.-.
[0011] In an aspect, the invention relates to a cartridge. The
cartridge includes a housing and at least one of a manganese
porphyrin catalyst or a manganese porphyrazine catalyst in the
housing. The cartridge is adapted to allow reactants to contact the
at least one of a manganese porphyrin catalyst or a manganese
porphyrazine catalyst.
[0012] In an aspect, the invention relates to a method of treating
a substance. The method includes generating chlorine dioxide by
exposing ClO.sub.2.sup.- to at least one of a manganese porphyrin
catalyst or a manganese porphyrazine catalyst. The method also
includes exposing the substance to the generated chlorine
dioxide.
[0013] In an aspect, the invention relates to a composition. The
composition includes a manganese porphyrazine compound having a
structure of formula VI:
##STR00001##
The "a" represents the oxidation state of the Mn and the oxidation
state can be any of the possible oxidation states. Each of A.sub.1,
A.sub.2, A.sub.3, A.sub.4, B.sub.1, B.sub.2, B.sub.3, B.sub.4,
C.sub.1, C.sub.2, C.sub.3, C.sub.4, D.sub.1, D.sub.2, D.sub.3, and
D.sub.4 are independently selected from N.sup.+--R.sub.n, N, C--H,
C--X, and C--R.sub.n. When N.sup.+--R.sub.n is selected, one or
zero group in each set of A.sub.1, B.sub.1, C.sub.1, and D.sub.1;
A.sub.2, B.sub.2, C.sub.2, and D.sub.2; A.sub.3, B.sub.3, C.sub.3,
and D.sub.3; or A.sub.4, B.sub.4, C.sub.4, and D.sub.4 is
N.sup.+--R.sub.n. When N is selected, two, one, or zero group in
each set of A.sub.1, B.sub.1, C.sub.1, and D.sub.1; A.sub.2,
B.sub.2, C.sub.2, and D.sub.2; A.sub.3, B.sub.3, C.sub.3, and
D.sub.3; or A.sub.4, B.sub.4, C.sub.4, or D.sub.4 is N. Each
R.sub.n is independently selected from the group consisting of H;
methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl; isobutyl;
CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where n1=5-20;
CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 and
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3. Ar is substituted or
unsubstituted phenyl, substituted or unsubstituted biphenyl, or
substituted or unsubstituted naphthyl and when Ar is the phenyl in
--CH.sub.2--Ar--X, (CH.sub.2).sub.mAr--X, or (CH.sub.2).sub.mAr--Y,
the X or Y is attached ortho-meta- or para to the --CH.sub.2--
attached to the pyridoporphyrazine. n is 1 to 10; m is 1 to 200; p
is 1 or 2; X is COOH, COO(alkyl.sub.1), CONH.sub.2,
CONH(alkyl.sub.1), CON(alkyl.sub.1).sub.2,
CO(CH.sub.2).sub.palkyl.sub.1, OPO.sub.3H.sub.2, PO.sub.3H.sub.2,
SO.sub.3H, NH.sub.2, N(alkyl.sub.1).sub.2, or
N(alkyl.sub.1).sub.3.sup.+, where alkyl.sub.1 is methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, or octyl. When
N.sup.+--R.sub.n is selected, one or zero group in each set of
A.sub.1, B.sub.1, C.sub.1, and D.sub.1; A.sub.2, B.sub.2, C.sub.2,
and D.sub.2; A.sub.3, B.sub.3, C.sub.3, and D.sub.3; or A.sub.4,
B.sub.4, C.sub.4, and D.sub.4 is N.sup.+--R.sub.n, R.sub.n may be
R.sub.15 and R.sub.15 is alkyl, CH.sub.2CH.sub.2OCH.sub.3,
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3, (CH.sub.2).sub.n--X,
(CH.sub.2).sub.n--Y, (CH.sub.2).sub.nAr--X, (CH.sub.2).sub.nAr--Y,
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3,
CH.sub.2CO.sub.2CH.sub.2CH.sub.3, (OCH.sub.2CH.sub.2).sub.m--X,
(OCH.sub.2CH.sub.2).sub.m--Y, Y.sub.2--X, or
Y.sub.2C(Z.sub.1).sub.3. Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3. Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3. Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3. Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3. Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y. Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2. W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH). W.sub.2 is OR.sub.16 and R.sub.16
is alkyl. Y.sub.2 is --(CH.sub.2).sub.nO--, --(CH.sub.2).sub.nNH--,
--(CH).sub.nS--; CH.sub.2CONH--, CH.sub.2COO--, or
CH.sub.2CO(CH.sub.2).sub.p--. L.sub.1 and L.sub.2 are,
independently absent, halide, oxo, aquo, hydroxo, CN, OPO.sub.3H,
or alcohol.
[0014] In an aspect, the invention relates to a method of treating
cyanide containing material. The method comprises exposing the
cyanide containing material to ClO.sub.2.sup.- and at least one
catalyst selected from the group consisting of a manganese
porphyrin catalyst or a manganese porphyrazine catalyst.
[0015] In an aspect, the invention relates to a kit for treating
cyanide containing material. The kit comprises at least one
catalyst selected from the group consisting of a manganese
porphyrin catalyst or a manganese porphyrazine catalyst. The kit
also comprises instructions to combine the at least one catalyst
with ClO.sub.2.sup.- in the presence of the cyanide containing
material.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The following detailed description of the preferred
embodiments of the present invention will be better understood when
read in conjunction with the appended drawings. For the purpose of
illustrating the invention, there are shown in the drawings
embodiments which are presently preferred. It is understood,
however, that the invention is not limited to the precise
arrangements and instrumentalities shown. In the drawings:
[0017] FIG. 1A illustrates the structure of MnTDMImP. FIG. 1B
illustrates the structure of MnTM-2,3-PyPz. Axial ligands may water
and hydroxo under exemplary conditions used.
[0018] FIG. 2A illustrates Abs. v. wavelength, FIG. 2B illustrates
a time resolved UV-vis spectra of ClO.sub.2 generation.
[0019] FIGS. 3A-B illustrate cartridges that may be employed as
portable chlorine dioxide generators.
[0020] FIG. 4 illustrates a GC-MS chromatogram of authentic DDA and
the extract of a reaction of DDA reacted with ClO.sub.2.
[0021] FIG. 5 illustrates a GC-MS chromatogram of DDA generated
when MO was present during the turnover reaction of MnTDMImP and
ClO.sub.2.sup.-.
[0022] FIGS. 6A-C illustrate (A and B) Spectroscopic changes
showing rapid and efficient production of chlorine dioxide upon
addition of the Mn catalyst to a sodium chlorite solution. (C)
Kinetic traces showing the very fast reaction rate for
Mn(III)TM-2,3-PyPz.
[0023] FIG. 7 illustrates the synthesis of two highly active
catalysts, MnTM-2,3-PyPz and MnTM-3,4-PyPz. These can be any of the
various regioisomers or a mixture thereof.
[0024] FIG. 8 illustrates the synthesis of Barrett and Hoffman's
octacationic pyridium substituted tetraazapophyrin.
[0025] FIG. 9 illustrates the synthesis of
(1-methyl-1H-imidazol-2-yl)acetonitrile.
[0026] FIG. 10 illustrates the manganese
octakis[(bismethyl)imidazoliumyl]tetraazaprophyrin.
[0027] FIGS. 11A and B illustrate (A) Rapid appearance of ClO2 (359
nm) from the MnTDMImP-catalyzed decomposition of ClO2- (10 mM) at
pH 6.8 with 0.1 mol % catalyst (445 nm) showing first 30 s of
reaction, 1 scan/s; and (B) Similar reaction with MnTM23PyPz (9 mM
sodium chlorite, 10 uM MnTM23PyPz, pH 4.7 100 mM acetate buffer,
showing the first 30 s of reaction, 1 scan/s).
[0028] FIG. 12 illustrates titration of 1.4 equivalents CN.sup.-
into ClO.sub.2 (359 nm) formed chlorite (260 nm) in 100% yield.
[0029] FIG. 13 illustrates .sup.13CNMR spectrum of the cyanate
anion in 10:90 H.sub.2O:D.sub.2O.
[0030] FIG. 14 illustrates the hydrolysis product of cyanate anion
observed in the study is CO.sub.2.
[0031] FIG. 15 illustrates the two hydrolysis products of cyanogen
observed in the study are oxalic acid and 1-cyanoformamide.
[0032] FIG. 16 illustrates the proposed modified reaction pathway
of MnPor/chlorite in the presence of cyanide.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] Certain terminology is used in the following description for
convenience only and is not limiting. The words "a" and "one," as
used in the claims and in the corresponding portions of the
specification, are defined as including one or more of the
referenced item unless specifically stated otherwise. The phrase
"at least one" followed by a list of two or more items, such as "A,
B, or C," means any individual one of A, B or C as well as any
combination thereof.
[0034] As described herein, it was found that exposing
ClO.sub.2.sup.- to at least one of a manganese porphyrin catalyst
or a manganese porphyrazine catalyst resulted in production of
chlorine dioxide (ClO.sub.2). Another innovation is the very rapid
depletion of added cyanide ion observed under the new variation of
the conditions in the production of ClO.sub.2. Unexpectedly,
cyanide enhances the activity of the catalysts described herein. An
advantage of this manganese catalyzed system therein is that the
acidity can be mild in embodiments, around pH 3-7 being optimal.
Cyanide ion enhances the activity of these manganese catalysts and
the cyanide is rapidly depleted from water solutions containing
chlorite ion and the manganese catalysts. This innovation and
improvement to the manganese-catalyzed process for the production
of chlorine dioxide is able to rapidly, efficiently and
catalytically remove cyanide ion and hydrogen cyanide from water.
This improvement further adds to the Green Chemistry aspect of this
catalysis and, at scale, may afford the user a carbon capture
credit as well.
[0035] An embodiment includes a method comprising contacting a
chlorite salt in a solvent such as water containing a catalytic
amount of a manganese porphyrin or manganese porphyrazine catalyst
using an acid source as the buffer system to maintain an acidic pH
(3-7). Under these conditions, cyanide ion and hydrogen cyanide are
rapidly depleted. Examples of the manganese porphoryn or manganese
porphyrazine catalyst can be found herein and in the references
incorporated herein. Embodiments include applying this method for
the decontamination of cyanide contaminated water, such as occur in
mining operations and other industrial processes.
[0036] An embodiment provides a method of generating chlorine
dioxide from chlorite ion by exposing chlorite ion to at least one
of a manganese porphyrin catalyst or manganese porphyrazine
catalyst. The catalyst may be water soluble. A mixture of manganese
porphyrin catalysts or manganese porphyrazine catalysts may be
present in a method herein. A mixture may be two or more species of
manganese porphyrin catalysts, two or more species of a manganese
porphyrazine catalyst, or at least one species of manganese
porphyrin catalyst plus at least one species of manganese
porphyrazine catalyst. The species of manganese porphyrin catalyst
may be selected from any manganese porphyrin compound herein. The
species of manganese porphyrazine compound may be selected from any
manganese porphyrazine compound herein. An embodiment provides a
cartridge that may be implemented as a chlorine dioxide generator.
An embodiment provides reagents for generating chlorine dioxide. An
embodiment provides a new chemical process that allows the
effective production of the disinfectant chlorine dioxide from
common chlorite salts. An embodiment provides a method, apparatus
and/or reagents to produce chlorine dioxide in rural areas that do
not have modern facilities. An embodiment includes a new catalytic
system that is able to produce gaseous chlorine dioxide on demand
from easily transportable chlorite salts. A method herein includes
contacting a chlorite salt in a solvent such as water containing a
catalytic amount of a manganese porphyrin manganese porphyrazine
catalyst. Chlorine dioxide is produced efficiently in minutes at
ambient temperature and pressure under mild, non-acidic conditions.
The catalyst may be free in solution. The catalyst can be
immobilized on a solid support, which may be readily available
clay. This may allow facile recovery of the catalyst and the
construction of a flow system for continuous production of chlorine
dioxide without electricity or other power sources. Embodiments
include treating a substance with the ClO.sub.2 generated by
another embodiment herein. The substance may be but is not limited
to a coolant, a liquid, water, air, a solid, or a surface. For
example, coolant for use in or in a coolant tower may be exposed to
ClO.sub.2 generated by another embodiment herein.
[0037] In an embodiment, a unique feature of a manganese porphyrin
catalyzed or manganese porphyrazine catalyzed method for the
production of chlorine dioxide is that added oxidants such as
hydrogen peroxide or chlorine are not necessary. Added reducing
agents such as methanol or hydrogen peroxide or added acids such as
sulfuric acid or hydrochloric acid are also unnecessary in an
embodiment. This is due to the fact that the catalyst is able to
utilize oxidation equivalents derived from the chlorite salt itself
at a range of pH that is either neutral, mildly acidic or mildly
basic. The net result for the reaction is a significant
simplification of the process since complicated metering or
potentially hazardous mixtures of hydrogen peroxide and either
chlorate or chlorite salts are unnecessary.
[0038] Advances in chemical catalysis have numerous intrinsic
advantages among the various strategies for mitigating pollution
and workforce hazards in chemical practice. Methods herein provide
an efficient, catalytic process for the generation of ClO.sub.2
from chlorite ion (ClO.sub.2.sup.-). A method herein may include a
manganese porphyrin catalyst. A method herein may include a
manganese porphyrazine catalyst. The catalyst may be the
water-soluble manganese porphyrin
tetrakis-5,10,15,20-(N,N-dimethylimidazolium)
porphyrinatomanganese(III), MnTDMImP (FIG. 1A). The catalyst may be
Mn TM-2,3-PyPz (FIG. 1B). The reaction may proceed rapidly and
efficiently under mild, ambient conditions.
[0039] Embodiments herein offer a potentially greener alternative
to the other commonly employed routes of ClO.sub.2 preparation. The
reactions available can be carried out in an aqueous system at
near-neutral pH under ambient pressure and temperature. In an
embodiment, a method of generating ClO.sub.2 and optionally of
treating a substance with the generated ClO.sub.2 includes
MnTDMImP-catalyzed decomposition of ClO.sub.2.sup.- (10 mM) at pH
6.8 with 0.1 mol %. Under these conditions, ClO.sub.2 may be formed
within seconds, and the reaction may be complete within minutes. In
an embodiment, a method of generating ClO.sub.2 and optionally of
treating a substance with the generated ClO.sub.2 includes the
catalyst MnTM23PyPz (9 mM sodium chlorite, 10 uM MnTM23PyPz, pH 4.7
in 100 mM acetate buffer). Other reaction conditions may be
provided in a method herein.
[0040] A manganese porphyrin catalyst or a manganese porphyrazine
catalyst may be present in a method, kit or cartridge herein at any
concentration from 0.05% to 1% by weight chlorite where %=[(weight
catalyst)/(weight chlorite)].times.100. A manganese porphyrin
catalyst or a manganese porphyrazine catalyst may be present at any
concentration in a sub-range within 0.05% to 1% by weight chlorite.
The lower value in the sub-range may be any value from 0.05% to
0.99% in 0.01% increments. The higher value in the sub-range may be
any value from 0.01% greater than the lower value to any value up
to and including 1% in 0.01% increments. A sub-range may be 0.1% to
0.5% by weight chlorite. When a mixture of manganese porphyrin
catalysts or manganese porphyrazine catalyst is present the "weight
catalyst" may be calculated as the combined weight of the catalysts
in the mixture. Catalyst concentrations outside of these ranges may
be provided in a method, kit or cartridge herein.
[0041] A manganese porphyrin catalyst or a manganese porphyrazine
catalyst may be present in a method, kit or cartridge herein at any
concentration from 1 to 500 micromolar. The concentration may be
any one integer value selected from the range 1 to 500 micromolar.
A manganese porphyrin catalyst or a manganese porphyrazine catalyst
may be present at concentration in a sub-range within 1 to 500
micromolar. The lower value in the sub-range may be any value from
1 micromolar to 499 micromolar in 1 micromolar increments. The
higher value in the sub-range may be any value from 1 micromolar
greater than the lower value to any value up to and including 500
micromolar in 1 micromolar increments. A sub-range may be 5-50
micromolar. When a mixture of manganese porphyrin catalysts or
manganese porphyrazine catalyst is present, the concentration may
be calculated based on the total amount of catalyst present.
Catalyst concentrations outside of these ranges may be provided in
a method, kit or cartridge herein.
[0042] As described below, a manganese porphyrin catalyst or a
manganese porphyrazine catalyst may be provided on a solid support.
A manganese porphyrin catalyst or a manganese porphyrazine catalyst
may be provided in a method, cartridge or kit herein at a
concentration of 0.1% to 5% catalyst by weight solid support where
%=[(weight catalyst)/(weight of the solid support)].times.100. A
manganese porphyrin catalyst or a manganese porphyrazine catalyst
may be present at any concentration in a sub-range within 0.1% to
5% by weight solid support. The lower value in the sub-range may be
any value from 0.1% to 5% in 0.1% increments. The higher value in
the sub-range may be any value from 0.1% greater than the lower
value to any value up to and including 5% in 0.1% increments. A
sub-range may be 0.1% to 1% by weight solid support. When a mixture
of manganese porphyrin catalysts or manganese porphyrazine catalyst
is present the "weight catalyst" may be calculated as the combined
weight of the catalysts in the mixture. Catalyst concentrations
outside of these ranges may be provided in a method, kit or
cartridge herein.
[0043] The chlorite concentration in a method, kit or cartridge
herein may be at any concentration from 0.5 millimolar to 1 molar.
The chlorite concentration may be any value in a sub-range from 0.5
millimolar to 1 molar. The lower value of the sub-range may be any
value from 0.5 to 999 millimolar in 1 millimolar increments. The
higher value in the sub-range may be any value from 1 millimolar
greater than the lower value to 1 molar in 1 millimolar increments.
A sub-range may be 1-500 millimolar. Chlorite concentrations
outside of these ranges may be provided in a method, kit or
cartridge herein.
[0044] A method herein may include reaction conditions at a pH of
1-14, or any value therein. The pH may be 2 to 8. The pH may be 4.5
to 7.2. The pH may be at a value in a range selected from any two
integer values selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, and 14. A kit or cartridge herein may include reagents or
conditions such that a reaction utilizing the kit or cartridge has
any of the above pH values. A method herein may be conducted at any
temperature allowing the reaction to proceed. The temperature may
be from the freezing point to the boiling point of the mixture. The
temperature may be from 0.degree. C. to 100.degree. C. The
temperature may be any integer value from 0.degree. C. to
100.degree. C. The temperature may be any value in a sub-range
between any two integer values from 0.degree. C. to 100.degree.
C.
[0045] Additives may be provided in a method, kit or cartridge
herein. Additives that may be provided include but are not limited
to acetate or phosphate buffer, and sodium chloride to maintain
ionic strength. Other additives to buffer or provide ionic strength
may also be provided. The acetate or phosphate buffer may be at any
concentration from 10 millimolar to 500 millimolar, or at any value
in a sub-range between any two integer values from 10 millimolar to
500 millimolar. The sodium chloride may be at any concentration
from 10 millimolar to 600 millimolar, or at any value in a
sub-range between any two integer values from 10 millimolar to 600
millimolar. Additive concentrations may be provide outside of these
ranges.
[0046] A manganese porphyrin catalyzed or manganese porphyrazine
method for the production of chlorine dioxide described here may
also produce bromine if sodium or potassium bromide, or some
similar bromide salt, is present as an additive. Bromide ion can
intercept and react with both reactive chlorine species such as
hypochlorite or chlorine dioxide and reactive manganese-oxo
complexes derived from the catalyst to produce bromine. Bromine is
similar in effectiveness to chlorine as a disinfectant and may have
advantages in the presence of chlorine dioxide or if all of the
chlorine dioxide is subsequently converted to bromine. Methods
herein include providing bromide ion in addition to chlorite ion
and at least one of a manganese porphyrin catalyst or manganese
porphyrazine catalyst. A kit or cartridge herein may also be
adapted to include bromide and be used to produce bromine. The
bromide concentration in a method, kit or cartridge herein may be
at any concentration from 0.5 millimolar to 2 molar. The bromide
concentration may be any value in a sub-range from 0.5 millimolar
to 2 molar. The lower value of the sub-range may be any value from
0.5 to 1999 millimolar in 1 millimolar increments. The higher value
in the sub-range may be any value from 1 millimolar greater than
the lower value to 2 molar in 1 millimolar increments. A sub-range
may be 1 to 500 millimolar, or 1 to 1000 millimolar. Bromide
concentrations outside of these ranges may be provided in a method,
kit or cartridge herein.
[0047] A composition may be provided having any one or more
catalyst herein and any one or more of the constituents above. The
concentration of catalyst and the any one or more constituent above
may be but are not limited to those listed above.
[0048] In addition, the use of a manganese porphyrin or
porphyrazine as a catalyst may avoid the necessity of auxiliary
oxidizers or acids, since the reaction is self-initiating. A method
herein may include removing ClO.sub.2 gas produced from a reaction
herein. The ClO.sub.2 may be removed from a reaction vessel; e.g.,
by using a simple apparatus. For example, gaseous ClO.sub.2 may be
removed from the reaction mixture by sparging with nitrogen, helium
or air. The sparging tube and optionally a frit may be placed at
the bottom of the reaction mixture and the ClO.sub.2 may be trapped
in cold water. The removed ClO.sub.2 may be used to oxidize a
substrate. The yield may be almost 60%. An efficiently-engineered
generator could take full advantage of the oxidizing power of the
ClO.sub.2. A heterogeneous version of this process would adapt well
to flow or cartridge systems for water purification and would
facilitate removal and recycling of the catalyst. Embodiments
provide such systems.
[0049] Porphyrin catalysts are discussed in U.S. application Ser.
No. 12/311,639 (published as US 2011-0306584 and issued as U.S.
Pat. No. 8,334,377 on Dec. 18, 2012), which was a 35 USC 371
national phase application of PCT/US2007/021453 filed Oct. 5, 2007
and is incorporated herein by reference as if fully set forth.
Porphyrin catalysts are also discussed in U.S. Pat. Nos. 6,448,239
and 6,969,707, which are incorporated herein by reference as if
fully set forth. The embodiments described herein extend the
knowledge of porphyrin catalysts and methods of use thereof. One or
more of the porphyrin catalysts in U.S. application Ser. No.
12/311,639 or U.S. Pat. Nos. 6,448,239 and 6,969,707 may be
utilized in an embodiment herein.
[0050] A manganese porphyrin catalyst for any embodiment herein may
have a structure of formula I:
##STR00002##
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be independently selected
from the group consisting of TM2PyP, TM4PyP, TDMImP, and TDMBImp,
which have a structure of formulas II, III, IV and V,
respectively:
##STR00003##
[0051] Examples of R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, and
R.sub.10 are provided below. R.sub.1, R.sub.2, R.sub.3, and R.sub.4
may be independently selected from any substituent such that the
resulting porphyrin has catalytic activity for the production of
chlorine dioxide from chlorite. R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10 may be independently selected from any
substituent such that the resulting porphyrin has catalytic
activity for the production of chlorine dioxide from chlorite.
Acronyms: TM2PyP, tetra-(N-methyl)-2-pyridyl porphyrin; TM4PyP,
tetra(Nmethyl)-4-pyridyl porphyrin; TDMImP,
tetra-(N,N-dimethyl)-imidazolium porphyrin; TDMBImP,
tetra(N,N-dimethyl)-benzimidazolium porphyrin; The superscripted
"a" represents oxidation state of the Mn. The oxidation state may
be any possible oxidation state. The oxidation state may be II, III
or IV in non-limiting examples; axial ligands are represented by
L.sub.1 and L.sub.2. Both Ls may be absent, or the complexes may be
either 5-coordinate with one L ligand or 6-coordinate with two L
ligands. The complexes may have charge balancing counter anions. A
non-limiting example of a charge balancing counter anion is
chloride ion. Further non-limiting examples of charge balancing
counter anions are provided below.
[0052] A manganes porphyrazine catalyst for any embodiment herein
may have a structure of formula VI:
##STR00004##
One or zero of A.sub.1, B.sub.1, C.sub.1, and D.sub.1 may be
N.sup.+--R.sub.n where the N.sup.+ occupies the position of
A.sub.1, B.sub.1, C.sub.1 or D.sub.1. One of A.sub.2, B.sub.2,
C.sub.2, and D.sub.1 may be N.sup.+--R.sub.n where the N.sup.+
occupies the position of A.sub.2, B.sub.2, C.sub.2, or D.sub.2. One
or zero of A.sub.3, B.sub.3, C.sub.3, and D.sub.3 may be
N.sup.+--R.sub.n where the N.sup.+ occupies the position of
A.sub.3, B.sub.3, C.sub.3, or D.sub.3. One or zero of A.sub.4,
B.sub.4, C.sub.4, and D.sub.4 may be N.sup.+--R.sub.n where the
N.sup.+ occupies the position of A.sub.4, B.sub.4, C.sub.4, or
D.sub.4. Two, one, or zero of A.sub.1, B.sub.1, C.sub.1, and
D.sub.1 may be N. One or zero of A.sub.2, B.sub.2, C.sub.2, and
D.sub.2 may be N. Two, one, or zero of A.sub.3, B.sub.3, C.sub.3
and D.sub.3 may be N. Two, one, or zero of A.sub.4, B.sub.4,
C.sub.4, and D.sub.4 may be N. Each of the remaining
A.sub.i-D.sub.i may be independently selected from C--H, C--X, and
C--R.sub.n where i is 1, 2, 3, or 4 and the C occupies the position
of A.sub.i, B.sub.i, C.sub.i or D.sub.i. X is as defined below with
respect to R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, and
R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and R.sub.14. R.sub.n
may be any one of R11-R14 as described below. Each R.sub.n may be
independently selected from any substituents such that the
resulting porphyrazine has catalytic activity for the production of
chlorine dioxide from chlorite. The superscripted "a" represents
the oxidation state of the Mn. The oxidation state may be any
possible oxidation state. The oxidation state may be II, III, or IV
in non-limiting examples. Axial ligands are represented by L.sub.1
and L.sub.2. Both L.sub.1 and L.sub.2 may be absent, or the
complexes may be either 5-coordinate with one L ligand or
6-coordinate with two L ligands. The complexes may have charge
balancing counter anions. A non-limiting example of a charge
balancing counter anion is chloride ion. Further non-limiting
examples of charge balancing counter anions are provided below.
[0053] An example where D.sub.1, D.sub.2, D.sub.3 and D.sub.4 are
N.sup.+--R.sub.11, N.sup.+--R.sub.12, N.sup.+--R.sub.13, and
N.sup.+--R.sub.14, respectively, is shown in formula VII:
##STR00005##
[0054] A regioisomer or positional substituted compound based on
formula VI may be provided as a porphyrazine catalyst herein. A
mixture of regioisomers or positional substituted compounds may be
provided as a porphyrazine catalyst herein. Non-limiting examples
of regioisomers, mixtures thereof or mixtures of positional
substituted compounds that may be provided as a phorphyrazine
catalyst are shown below in formulas VIII through XIV.
##STR00006##
Due to the method of synthesis, mixed isomers can be prepared by
using a mixture of dicyanoolefins as starting materials and a
mixture of alkylating agents R.sub.11-LG, R.sub.12-LG, R.sub.13-LG,
and R.sub.14-LG with LG being a typical leaving group. Examples of
leaving groups include but are not limited to iodide, triflate,
bromide and tosylate. Formulas IX and X show two of four possible
regioisomers.
##STR00007##
Formulas XI and XII show two of four possible additional
regioisomers.
##STR00008##
Formulas XIII and XIV show two of four possible additional
regioisomers.
##STR00009##
Any possible regioisomer or combinations thereof of any of the
above phorphyrazine compounds may be provided as a porphyrazine
catalyst in embodiments herein.
[0055] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from H; methyl; ethyl;
propyl; isopropyl; n-butyl; sec-butyl; isobutyl;
CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where n1=5-20;
CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20; or
--CH.sub.2--Ar--X where Ar may be phenyl, biphenyl or naphthyl. For
the phenyl case, X may be attached ortho-meta- or para to the
--CH.sub.2-- attached to the pyridoporphyrazine. X is described
below.
[0056] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from H; (CH.sub.2).sub.n--X
where n is 1 to 10 and X is COOH, COO(alkyl.sub.1), CONH.sub.2,
CONH(alkyl.sub.1), CON(alkyl.sub.1).sub.2,
CO(CH.sub.2).sub.palkyl.sub.1, OPO.sub.3H.sub.2, PO.sub.3H.sub.2,
SO.sub.3H, NH.sub.2, N(alkyl.sub.1).sub.2, or
N(alkyl.sub.1).sub.3.sup.+, where alkyl.sub.1 is methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, or octyl. Any one or more of
R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, and R.sub.10, or
R.sub.11, R.sub.12, R.sub.13, and R.sub.14 may be independently
selected from alkyl, CH.sub.2CH.sub.2OCH.sub.3,
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3, (CH.sub.2).sub.n--Y,
(CH.sub.2)--Ar--X, (CH.sub.2)--Ar--Y,
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3,
CH.sub.2CO.sub.2CH.sub.2CH.sub.3, (OCH.sub.2CH.sub.2).sub.m--X,
(OCH.sub.2CH.sub.2).sub.m--Y, Y.sub.2--X, or
Y.sub.2C(Z.sub.1).sub.3. Z.sub.1 may be
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3. Z.sub.2 may be
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3 and Z.sub.4
may be CH.sub.2OCH.sub.2CH.sub.2X, or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3. Z.sub.5 may be
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3 and Z.sub.6
may be
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y. p may be 1 or 2. Y may be OH or
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2, where W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH) and W.sub.2 is OR.sub.16, and
R.sub.16 is alkyl. m is 1 to 200. Y.sub.2 may be
--(CH.sub.2).sub.nO--, --(CH.sub.2).sub.nNH--, --(CH).sub.nS--;
CH.sub.2CONH--, CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p--,
where p is 1 or 2, and n is 1 to 10.
[0057] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from H,
(CH.sub.2).sub.mAr--X or (CH.sub.2).sub.mAr--Y, where Ar is
substituted or unsubstituted phenyl or substituted or unsubstituted
naphthyl, m is 1 to 200, and X and Y are as defined above.
[0058] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from (CH.sub.2).sub.n--Y,
where n is 1 to 10 and Y is as defined above.
[0059] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from CH.sub.2CONH--Y,
CH.sub.2COO--Y, or CH.sub.2CO(CH.sub.2).sub.P--Y, where p is 1 or 2
and Y is as defined above.
[0060] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from
(OCH.sub.2CH.sub.2).sub.m--Y, where Y is as defined above.
[0061] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from
(OCH.sub.2CH.sub.2).sub.m--X, where m is 1 to 200, and X is as
defined above.
[0062] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from Y.sub.2--X, where X and
Y.sub.2 are as defined above.
[0063] Any one or more of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10, or R.sub.11, R.sub.12, R.sub.13, and
R.sub.14 may be independently selected from
--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 or
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3.
[0064] In an embodiment, one of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, or R.sub.10 is selected from one of the examples below
other than H, and the remaining ones of R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, or R.sub.10 are H. In an embodiment, one of
R.sub.11, R.sub.12, R.sub.13 or R.sub.14 is selected from one of
the examples below other than H, and the remaining ones of
R.sub.11, R.sub.12, R.sub.13 or R.sub.14 are H.
[0065] In some embodiments, a porphyrin or porphyrazine catalyst is
provided in association with suitable ligands (L.sub.1 and L.sub.2)
and/or charge neutralizing anions. L.sub.1 and L.sub.2 can be the
same or different, and one or more may be absent. The structures
above showing L.sub.1 and L.sub.2 thus include the possibility that
L.sub.1 and L.sub.2 can be the same or different, and one or more
may be absent. Ligands and charge neutralizing anions can be
derived from any monodentate or polydentate coordinating ligand or
ligand system or the corresponding anion thereof. Ligands and
charge neutralizing anions may be independently selected from the
group consisting of halide, oxo, aquo, hydroxo, alcohol, phenol,
dioxygen, peroxo, hydroperoxo, alkylperoxo, arylperoxo, ammonia,
alkylamino, arylamino, heterocycloalkyl amino, heterocycloaryl,
amino, amine oxides, hydrazine, alkyl hydrazine, aryl hydrazine,
nitric oxide, cyanide, cyanate, thiocyanate, isocyanate,
isothiocyanate, alkyl nitrite, aryl nitrile, alkyl isonitrile, aryl
isozutrile, nitrate, nitrite, azido, alkyl sulfonic acid, aryl
sulfonic acid, alkyl sulfoxide, aryl sulfoxide, alkyl aryl
sulfoxide, alkyl sulfenic acid, aryl sulfenic acid, alkyl sulfuric
acid, aryl sulfinic acid, alkyl thiol carboxylic acid, aryl thiol
carboxylic acid, alkyl thiol thiocarboxylic acid, aryl thiol
thiocarboxylic acid, alkyl carboxylic acid, aryl carboxylic acid,
urea, alkyl urea, aryl urea, alkyl aryl urea, thiourea, alkyl
thiourea, aryl thiourea, alkyl aryl thiourea, sulfate, sulfite,
bisulfate, bisulfite, thiosulfate, thiosulfite, hydrosulfite, alkyl
phosphine, aryl phosphine, alkyl phosphine oxide, aryl phosphine
oxide, alkyl aryl phosphine oxide, alkyl phosphine sulfide, aryl
phosphine sulfide, alkyl aryl phosphine sulfide, alkyl phosphonic
acid, aryl phosphonic acid, alkyl phosphinic acid, aryl phosphinic
acid, alkyl phosphinous acid, aryl phosphinous acid, phosphate,
thiophosphate, phosphite, pyrophosphite, triphosphate, hydrogen
phosphate, dihydrogen phosphate, alkyl guanidino, aryl guanidino,
alkyl aryl guanidino, alkyl carbamate, aryl carbamate, alkyl aryl
carbamate, alkyl thiocarbamate, aryl thiocarbamate, alkyl aryl
thiocarbamate, alkyl ditbiocarbamate, aryl dithiocarbamate, alkyl
aryl dithiocarbamate, bicarbonate, carbonate* perchlorate,
chlorate, chlorite, hypochlorite, perbromate, bromate, bromite,
hypobromite, tetrahalomanganate, tetrafluoroborate,
hexafluorophosphate, hexafluoroanitmonate, hypophosphite, iodate,
periodate, metaborate, tetraaryl borate, tetra alkyl borate,
tartrate, salicylate, succinate, citrate, ascorbate, saccharinate,
amino acid, hydroxamic acid, thiotosylate, and anions of ion
exchange resins, or systems. When the charge neutralizing complex
has a net positive charge, then a negatively charged counter ion
may be provided. When the charge neutralizing complex has net
negative charge, a counter ion selected from alkaline and alkaline
earth cations, organic cations, alkyl cations or alkylaryl ammonium
cations may be provided. Ligands L.sub.1 and L.sub.2 may be
independently selected from halide, oxo, aquo, hydroxo and alcohol.
Anionic counterfoils may be halide ions. Halide ions include
fluoro, chloro, bromo or iodo ions. Ligands and counterions may be
the same or different. For example, a metallic complex may have one
or two chloro axial ligands and 1, 2, 3, or 4 chloride ions as
charge neutralizing anions.
[0066] Non-limiting examples of "alkyl" include a straight-chain or
branched-chain alkyl radical containing from 1 to 22 carbon atoms,
or from 1 to 18 carbon atoms, or from 1 to 12 carbon atoms. Further
non-limiting examples of "alkyl" include methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl,
iso-amyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl,
hexadecyl, octadecyl and eicosyl. Lower alkyl refers to a
straight-chain or branched-chain alkyl radical containing from 1 to
6 carbon atoms.
[0067] Non-limiting examples of "aryl" include a phenyl or naphthyl
radical. The pheny or napthyl radicacl may carry one or more
substituents selected from alkyl, cycloalkyl, cycloalkenyl, aryl,
heterocycle, alkoxyaryl, alkaryl, alkoxy, halogen, hydroxy, amine,
cyano, nitro, alkylthio, phenoxy, ether, trifluoromethyl, phenyl,
p-tolyl, 4-methoxy-phenyl, 4-(tert-butoxy)phenyl, 4-fluorophenyl,
4-chiorophenyl, 4-hydroxyphenyl, and 1-naphthyl, 2-naphthyl, or
similar substituents.
[0068] Non-limiting examples of "aralkyl" include an alkyl or
cycloalkyl radical in which one hydrogen atom is replaced by an
aryl radical. One example is benzyl, 2-phenylethyl.
[0069] "Heterocyclic" means ring structures containing at least one
other kind of atom, in addition to carbon, in the ring. The most
common of the other kinds of atoms include nitrogen, oxygen and
sulfur. Examples of heterocycles include, but are not limited to,
pyrrolidinyl, piperidyl, imidazolidinyl, tetrahydrofuryl,
tetrahydrothienyl, furyl, thienyl, pyridyl, quinolyl, isoquinolyl,
pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl,
pyrazolyl, pyridinyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl
and tetrazolyl groups.
[0070] Non-limiting examples of "cycloalkyl" include a cycloalkyl
radical containing from 3 to 10, or from 3 to 8, or from 3 to 6
carbon atoms. Further non-limiting examples of such cycloalkyl
radicals include, but are not limited to, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and
perhydronaphthyl.
[0071] The term "cycloalkenyl" means a cycloalkyl radical having
one or more double bonds. Examples include, but are not limited to,
cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, and
cyclooctadienyl.
[0072] Embodiments also include any isomer of the any of the above
porphyrin or porphyrazine catalysts or a method, kit or cartridge
involving the same. Also included are tautomers of the compounds or
a method, kit or cartridge involving the tautomers. Tautomers may
include compounds wherein one or more of the various R groups are
simple variations of the substituents as defined therein, or
substituents which are a higher alkyl group than that indicated. In
another example, anions having a charge other than 1 can be used
instead of anions having a charge of 1. Examples of anions having a
charge other than 1 include carbonate, phosphate, and hydrogen
phosphate. Using anions having a charge other than 1 will result in
a slight modification of the general formula for the compounds set
forth above, but the skilled artisan will recognize the slight
modification.
[0073] Embodiments herein provide an efficient, catalytic process
for the generation of ClO.sub.2 from chlorite ion
(ClO.sub.2.sup.-). In an embodiment, the method includes contacting
a chlorine salt in a solvent containing a catalytic amount of a
particular manganese porphyrin or N-akylpyridinium porphyrazine
catalysts. The solvent may be water. Chlorine dioxide is produced
efficiently in minutes at ambient temperature and pressure under
mild, non-acidic conditions. The catalyst may be immobilized on a
readily available clay. This allows facile recovery of the catalyst
and would allow the construction of a flow system for continuous
production of chlorine dioxide without electricity or other power
sources.
[0074] Referring to FIGS. 1A-B, MnTDMImP was previously found to be
the most effective porhyrin catalyst. The rationale for the high
activity is the strong electron withdrawing effect of the pendant
imidazolium substituent since it modulates both the manganese redox
potential and the pKa of water and hydroxide bond to the metal
center. Very recent data has shown that the readily available
manganese porphyrazine catalyst Mn(III)TM-2,3-PyPz (either as
separated regiosomers or a mixture thereof and the corresponding
3,4-isomer) are even more potent catalysts than MnTDMImp, with
forty-fold higher activity. See Table 1, below. Related
pthalocyanines, as well as Mn(II) and Mn(IV) oxidation states may
be provided in embodiments herein.
TABLE-US-00001 TABLE 1 MnTM-2,3-PyPz is 40-fold faster than
MnTDMImP k.sub.RDS Compound pH (M.sup.-1 s.sup.-1) MnTDMImP 4.7
1.36 .times. 10.sup.2 MnTDMImP 6.8 5.62 .times. 10.sup.1
MnTM-2,3-PyPz 4.5 5.29 .times. 10.sup.3
[0075] In any method, kit, cartridge or composition herein, the
following may be provided. A chlorite source may provided in any
suitable form. A chlorite source may be any chlorite salt.
Non-limiting examples of chlorite salts that may be provided as a
chlorite source are sodium chlorite, potassium chlorite, calcium
chlorite and magnesium chlorite. A catalyst herein may be provided
on a solid support. The solid support may be a clay. The solid
support may be montmorillonite. The solid support may be but is not
limited to silica, alumina, glass beads, functionalized polystyrene
or organic polymers. The ClO.sub.2.sup.- may be adsorbed on a
substance, which may be but is not limited to clay, silica, alumina
or organic polymers.
[0076] A method herein includes generating chlorine dioxide by
exposing ClO.sub.2.sup.- to at least one of a manganese porphyrin
catalyst or a manganese porphyrazine catalyst. The manganese
porphyrin catalyst may be any compound that catalyzes the reaction
of ClO.sub.2.sup.- to ClO.sub.2. The manganese porphyrin catalyst
may but is not limited to any of the manganese porphyrin compounds
described herein. The manganese poyphyrazine catalyst may be any
compound that catalyzes the reaction of ClO.sub.2.sup.- to
ClO.sub.2. The manganese porphyrazine catalyst may but is not
limited to any of the manganese porphyrazine compounds described
herein. The method may include providing a chlorite source. The
chorite source may be a chlorite salt. The chlorite source may be
but is not limited to sodium chlorite, potassium chlorite, calcium
chlorite or magnesium chlorite. The chlorite salt may be mixed with
a solid filler. The chlorite source may be adsorbed on a substance.
The substance may be but is not limited to clay, silica, alumina or
organic polymers.
[0077] The at least one of the manganese porphyrin catalyst or a
manganese porphyrazine catalyst is adsorbed on a solid support. The
solid support may be but is not limited to one or more of clay,
silica, alumina, glass beads, functionalized polystyrene or organic
polymers.
[0078] A method herein includes treating a substance with the
ClO.sub.2 generated by any other method herein, or by any reaction
or use of any kit or cartridge herein. The substance may be but is
not limited to water, air, a solid, a surface, cooling liquid,
cooling liquid in a cooling tower, surfaces where biofilms may
develop or have developed, food processing equipment, food
products, and oral hygiene products.
[0079] An embodiment includes a cartridge system for producing
chlorine dioxide from chlorite salts. The cartridge may be utilized
in any manner apparent herein. The cartridge may be utilized as a
portable chlorine dioxide generator, or a cartridge system for
water purification with catalytic, in situ production of chlorine
dioxide from chlorite salts. A cartridge type generator of chlorine
dioxide using a fixed bed flow type reactor is described. Sodium
chlorite, or other typical chlorite salts can be used either pure,
mixed with a solid filler or adsorbed on a substance. The substance
may be but is not limited to clay, silica, alumina, or organic
polymers. A manganese porphyrin and/or manganese porphyrazine
catalyst may also be adsorbed on a solid support. The solid support
may be but is not limited to clay, silica, alumina, glass beads,
functionalized polystyrene or organic polymers.
[0080] Referring to FIG. 3A, a cartridge 300 may include a housing
305, and a first compartment 320 including a chlorite salt. The
chlorite salt may be but is not limited to sodium chlorite. The
cartridge 300 may have a second compartment 330 having a manganese
porphyrin catalyst and/or a manganese porphyrazine catalyst. Any
manganese porphyrin or manganese porphyrazine catalyst may be
provided in a cartridge, including any one or more of those listed
herein. A fluid may be provided through an input 310 into the
cartridge 300 and into the first compartment 320. The fluid may be
water, or a solution made with water as the solvent. The chlorite
salt may be dissolved in the fluid and then flow into the second
compartment 330. The reaction to produce chlorine dioxide may occur
in the cartridge 300. Fluid and/or chlorine dioxide may be provided
through output 340. The cartridge may include additional
constituents that could support the reaction to produce chlorine
dioxide. For example, the cartridge could include buffer
constituents.
[0081] As shown in FIG. 3A, the chlorite and catalyst may be in
separate sections (as shown). Alternatively, the chlorite salt and
catalyst could be mixed in a single section, or in a cartridge
having no separate compartments. An interface; e.g., interface 345,
between catalyst and chlorite salt may be included in a cartridge.
The interface may be solid. The interface may be a complete
barrier, or may have holes allowing retention of solid material. An
interface could be made of a material that will allow mixing of the
chlorite salt and catalyst upon a mechanical disruption. The
mechanical disruption could be breaking of the interface. The
mechanical disruption may be dissolution or other structural
failure of the interface in the liquid. Holes in the interface may
be provided in a configuration and/or size that does not allow
passage of the chlorite salt or catalyst, but will allow passage of
the fluid and solutes therein. The catalyst and chlorite
compartments may be one unit, or two separate pieces that can be
combined when in use. In the latter case, reuse of a catalyst bed
may be more convenient. Alternatively, the cartridge may contain
only the manganese porphyrin and/or manganese porphyrazine catalyst
and the chlorite may be added to the fluid that is then allowed to
flow over the catalyst bed.
[0082] The design of a cartridge may allow the production of either
concentrated chlorine dioxide solutions to be later diluted into
water that is to be treated or dilute (ppb-ppm) chlorine dioxide
solutions that may be suitable for drinking or other such uses of
water that has been decontaminated in this manner. An ion exchange
cartridge may be inserted after the catalytic manganese flow
reactor to reduce any effluent ClO.sub.X salts. The cartridge
system may also be fitted with a sparging tube or frit to remove
pure ClO.sub.2 from the reaction stream. The desired concentration
of ClO.sub.2, concentrated or dilute, can be obtained by varying
the catalyst loading, chlorite salt concentration and flow rate of
the chlorite solution over the catalyst bed.
[0083] Referring to FIG. 3B, a cartridge 350 is illustrated. The
cartridge 350 includes a housing 355, an input 360, an optional
additional reagent input 365, an optional gas vent 370, and an
output 375. Fluid may be delivered into the cartridge 350 through
the input 360. The cartridge 350 may include a manganese porphyrin
and/or manganese porphyrazine catalyst within housing 355.
Optionally, the cartridge 350 includes a compartment 380 including
a manganese porphyrin and/or manganese porphyrazine catalyst. A
chlorite solution may be provided as the fluid. Alternatively, a
chlorite salt may be provided within the cartridge 350. For
example, the chlorite salt may be provided in optional compartment
390. A catalyst in cartridge 350 may be provided absorbed on a
solid support. A chlorite source in cartridge 350 may be provided
absorbed on a substance and/or mixed with a filler.
[0084] An embodiment includes a cartridge having any configuration
that allows containment of a catalyst and/or a chlorite salt, and
then passage of a fluid through the cartridge. An embodiment
includes a cartridge like that of U.S. Pat. No. 6,740,223, which is
incorporated herein by reference as if fully set forth, but where
the electrode elements are replaced by a catalyst and/or chlorite
salt herein.
[0085] A cartridge may be made of any suitable material. The
suitable material may include but is not limited to glass, wood,
metal, plastic, polycarbonate, and polyallomer. Any method herein
may be conducted by implemented any cartridge herein. In an
embodiment, fluid is pumped through a cartridge including a
chlorite source and including a manganese porphyrin and/or
manganese porphyrazine catalyst. The fluid may be water. In an
embodiment, a chlorite source is provided to a fluid, and the fluid
plus chlorite source is pumped through a cartridge including a
manganese porphyrin and/or manganese porphyrazine catalyst.
[0086] An embodiment includes a kit for producing chlorine dioxide.
Embodiments include a kit for sanitizing a substance. A kit may
include any catalyst herein. A kit may include a chlorite source
herein. A kit may include instructions to contact the chlorite
source with the catalyst. Any cartridge herein may be provided in a
kit. The instructions may include details of the reaction
conditions as provided herein, and/or instructions for using any
cartridge herein. The kit may include instructions to conduct any
one or more method herein.
[0087] An embodiment includes a compound selected from
Mn.sup.IIITDMImP, Mn.sup.IIITM-2,3-PyPz, any isomeric form of
Mn.sup.IIITM-2,3-PyPz, any manganese porphyrin catalyst herein, any
isomeric form of any manganese porphyrin catalyst herein, any
manganese porphyrazine catalyst herein, or any isomeric form of any
manganese pophyrazine catalyst herein.
[0088] An embodiment includes a method of treating cyanide
containing material. The method may comprising exposing the cyanide
containing material to ClO.sub.2.sup.- and at least one catalyst
selected from the group consisting of a manganese porphyrin
catalyst or a manganese porphyrazine catalyst. The at least one
catalyst may be selected from any catalyst herein. The
ClO.sub.2.sup.- may be provided from at least one substance
selected from the group consisting of chlorite salts. The
ClO.sub.2.sup.- may be provided from sodium chlorite, potassium
chlorite, calcium chlorite or magnesium chlorite. The
ClO.sub.2.sup.- may be mixed with a solid filler, or adsorbed on at
least one substance. The at least one substance may be selected
from clay, silica, alumina, or organic polymers. At least one of
the manganese porphyrin catalyst or a manganese porphyrazine
catalyst may be adsorbed on a solid support. The solid support may
be clay, silica, alumina, glass beads, functionalized polystyrene
or organic polymers. The method may include any of the conditions
described herein with respect to a method of generating chloring
dioxide with the addition of the cyanide containing material. The
cyanide may be in the form of cyanide ions or hydrogen cyanide.
[0089] An embodiment includes a kit for treating cyanide containing
material. The kit may comprise a at least one catalyst selected
from a manganese porphyrin catalyst or a manganese porphyrazine
catalyst. The kit may include instructions to combine the at least
one catalyst with ClO.sub.2.sup.- in the presence of the cyanide
containing material. The at least one catalyst may be selected from
any catalyst herein. The ClO.sub.2.sup.- may be provided from at
least one of sodium chlorite, potassium chlorite, calcium chlorite
or magnesium chlorite. The ClO.sub.2.sup.- may be mixed with a
solid filler. The ClO.sub.2.sup.- may be adsorbed on at least one
substance selected from the group consisting of clay, silica,
alumina and organic polymers. At least one of the manganese
porphyrin catalyst or a manganese porphyrazine catalyst may
adsorbed on a solid support. The solid support may include a
substance selected from clay, silica, alumina, glass beads,
functionalized polystyrene or organic polymers. The kit may further
include any other substance from any kit for generating chloring
dioxide herein. The cyanide may be in the form of cyanide ions or
hydrogen cyanide.
[0090] Embodiments include any method of generating chloring
dioxide, kit for generating chlorine dioxide, cartridge, method of
treating a substance, or composition herein adapted to treating
cyanide containing material by being conducted or utilized in the
presence of the cyanide containing material. The cyanide may be in
the form of cyanide ions or hydrogen cyanide.
EMBODIMENTS
[0091] The following list includes particular embodiments. But the
list is not limiting and does not exclude alternate embodiments, as
would be appreciated by one of ordinary skill in the art.
[0092] 1. A method of treating cyanide containing material
comprising exposing the cyanide containing material to
ClO.sub.2.sup.- and at least one catalyst selected from the group
consisting of a manganese porphyrin catalyst or a manganese
porphyrazine catalyst.
[0093] 2. The method of embodiment 1, wherein the at least one
catalyst includes a manganese porphyrin catalyst having a structure
of formula I:
##STR00010##
[0094] wherein the a is the oxidation state II, III or IV of the Mn
and R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently
selected from the group consisting of TM2PyP, TM4PyP, TDMImP, and
TDMBImp, which have a structure of formulas II, III, IV and V,
respectively:
##STR00011##
[0095] and at least one of R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, and R.sub.10 are independently selected from the group
consisting of H; methyl; ethyl; propyl; isopropyl; n-butyl;
sec-butyl; isobutyl; CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where
n1=5-20; CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2).sub.nAr--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; or
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p-- where
[0096] Ar is substituted or unsubstituted phenyl, substituted or
unsubstituted biphenyl, or substituted or unsubstituted naphthyl
and when Ar is the phenyl in --CH.sub.2--Ar--X,
(CH.sub.2).sub.mAr--X, or (CH.sub.2).sub.mAr--Y, the X or Y is
attached ortho-meta- or para to the --CH.sub.2-- attached to
pyridoporphyrazine;
[0097] n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH,
COO(alkyl.sub.1), CONH.sub.2, CONH(alkyl.sub.1),
CON(alkyl.sub.1).sub.2, CO(CH.sub.2).sub.palkyl.sub.1,
OPO.sub.3H.sub.2, PO.sub.3H.sub.2, SO.sub.3H, NH.sub.2,
N(alkyl.sub.1).sub.2, or N(alkyl.sub.1).sub.3.sup.+, where
alkyl.sub.1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
or octyl; and
[0098] L.sub.1 and L.sub.2 are, independently absent, halide, oxo,
aquo, hydroxo, CN, OPO.sub.3H, or alcohol.
[0099] 3. The method of embodiment 2, wherein R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are TDMBImp.
[0100] 4. The method of embodiment 2, wherein R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are TM2PyP or R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are TM4PyP.
[0101] 5. The method of embodiment 1, wherein the at least one
catalyst includes a manganese porphyrazine catalyst having a
structure of formula VI:
##STR00012##
[0102] wherein a is the oxidation state II, III or IV of the Mn and
each of A.sub.1, A.sub.2, A.sub.3, A.sub.4, B.sub.1, B.sub.2,
B.sub.3, B.sub.4, C.sub.1, C.sub.2, C.sub.3, C.sub.4, D.sub.1,
D.sub.2, D.sub.3 and D.sub.4 are independently selected from
N.sup.+--R.sub.n, N, C--H, C--X, and C--R.sub.n;
[0103] when N.sup.+--R.sub.n is selected, only one in each set of
A.sub.1, B.sub.1, C.sub.1, and D.sub.1; A.sub.2, B.sub.2, C.sub.2,
and D.sub.2; A.sub.3, B.sub.3, C.sub.3, and D.sub.3; or A.sub.4,
B.sub.4, C.sub.4, and D.sub.4 is N.sup.+--R.sub.n;
[0104] when N is selected, only one in each set of A.sub.1,
B.sub.1, C.sub.1, and D.sub.1; A.sub.2, B.sub.2, C.sub.2, and
D.sub.2; A.sub.3, B.sub.3, C.sub.3, and D.sub.3; or A.sub.4,
B.sub.4, C.sub.4, or D.sub.4 is N;
[0105] each R.sub.n is independently selected from the group
consisting of H; methyl; ethyl; propyl; isopropyl; n-butyl;
sec-butyl; isobutyl; CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where
n1=5-20; CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 and
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2).sub.nAr--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; o
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p--; and where
[0106] Ar is substituted or unsubstituted phenyl, substituted or
unsubstituted biphenyl, or substituted or unsubstituted naphthyl
and when Ar is the phenyl in --CH.sub.2--Ar--X,
(CH.sub.2).sub.mAr--X, or (CH.sub.2).sub.mAr--Y, the X or Y is
attached ortho-meta- or para to the --CH.sub.2-- attached to
pyridoporphyrazine;
[0107] n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH,
COO(alkyl.sub.1), CONH.sub.2, CONH(alkyl.sub.1),
CON(alkyl.sub.1).sub.2, CO(CH.sub.2).sub.palkyl.sub.1,
OPO.sub.3H.sub.2, PO.sub.3H.sub.2, SO.sub.3H, NH.sub.2,
N(alkyl.sub.1).sub.2, or N(alkyl.sub.1).sub.3.sup.+, where
alkyl.sub.1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
or octyl; and
[0108] L.sub.1 and L.sub.2 are, independently absent, halide, oxo,
aquo, hydroxo, CN, OPO.sub.3H, or alcohol.
[0109] 6. The method of any one or more of embodiments 1-5, wherein
the ClO.sub.2.sup.- is provided from at least one substance
selected from the group consisting of chlorite salts.
[0110] 7. The method of any one or more of embodiments 1-6, wherein
the ClO.sub.2.sup.- is provided from at least one substance
selected from the group consisting of sodium chlorite, potassium
chlorite, calcium chlorite and magnesium chlorite.
[0111] 8. The method of any one or more of embodiments 1-7, wherein
the ClO.sub.2.sup.- is mixed with a solid filler.
[0112] 9. The method of any one or more of embodiments 1-8, wherein
the ClO.sub.2.sup.- is adsorbed on at least one substance selected
from the group consisting of clay, silica, alumina and organic
polymers.
[0113] 10. The method of any one or more of embodiments 1-9,
wherein at least one of the manganese porphyrin catalyst or a
manganese porphyrazine catalyst is adsorbed on a solid support.
[0114] 11. The method of any one or more of embodiments 1-10,
wherein the solid support includes a substance selected from the
group consisting of clay, silica, alumina, glass beads,
functionalized polystyrene or organic polymers.
[0115] 12. A kit for treating cyanide containing material
comprising at least one catalyst selected from the group consisting
of a manganese porphyrin catalyst or a manganese porphyrazine
catalyst and instructions to combine the at least one of a
manganese porphyrin catalyst or a manganese porphyrazine catalyst
with ClO.sub.2.sup.- in the presence of the cyanide containing
material.
[0116] 13. The kit of embodiment 12, wherein the at least one
catalyst includes a manganese porphyrin catalyst having a structure
of formula I:
##STR00013##
wherein a is the oxidation state II, III or IV of the Mn and
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected
from the group consisting of TM2PyP, TM4PyP, TDMImP, and TDMBImp,
which have a structure of formulas II, III, IV and V,
respectively:
##STR00014##
and at least one of R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9,
and R.sub.10 are independently selected from the group consisting
of H; methyl; ethyl; propyl; isopropyl; n-butyl; sec-butyl;
isobutyl; CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where n1=5-20;
CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2)--Ar--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; or
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p-- where
[0117] Ar is substituted or unsubstituted phenyl, substituted or
unsubstituted biphenyl, or substituted or unsubstituted naphthyl
and when Ar is the phenyl in --CH.sub.2--Ar--X,
(CH.sub.2).sub.mAr--X, or (CH.sub.2).sub.mAr--Y, the X or Y is
attached ortho-meta- or para to the --CH.sub.2-- attached to
pyridoporphyrazine;
[0118] n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH,
COO(alkyl.sub.1), CONH.sub.2, CONH(alkyl.sub.1),
CON(alkyl.sub.1).sub.2, CO(CH.sub.2).sub.palkyl.sub.1,
OPO.sub.3H.sub.2, PO.sub.3H.sub.2, SO.sub.3H, NH.sub.2,
N(alkyl.sub.1).sub.2, or N(alkyl.sub.1).sub.3.sup.+, where
alkyl.sub.1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
or octyl; and
[0119] L.sub.1 and L.sub.2 are, independently absent, halide, oxo,
aquo, hydroxo, CN, OPO.sub.3H, or alcohol.
[0120] 14. The kit of embodiment 13, wherein R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are TDMBImp.
[0121] 15. The kit of embodiment 13, wherein R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are TM2PyP or R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are TM4PyP.
[0122] 16. The kit of embodiment 12, wherein the at least one
catalyst includes a manganese porphyrazine catalyst having a
structure of formula VI:
##STR00015##
[0123] wherein a is the oxidation state II, III or IV of the Mn and
each of A.sub.1, A.sub.2, A.sub.3, A.sub.4, B.sub.1, B.sub.2,
B.sub.3, B.sub.4, C.sub.1, C.sub.2, C.sub.3, C.sub.4, D.sub.1,
D.sub.2, D.sub.3 and D.sub.4 are independently selected from
N.sup.+--R.sub.n, C--H, C--X, and C--R.sub.n;
[0124] when N.sup.+--R.sub.n is selected, only one in each set of
A.sub.1, B.sub.1, C.sub.1, and D.sub.1; A.sub.2, B.sub.2, C.sub.2,
and D.sub.2; A.sub.3, B.sub.3, C.sub.3, and D.sub.3; or A.sub.4,
B.sub.4, C.sub.4, and D.sub.4 is N.sup.+--R.sub.n;
[0125] when N is selected, only one in each set of A.sub.1,
B.sub.1, C.sub.1, and D.sub.1; A.sub.2, B.sub.2, C.sub.2, and
D.sub.2; A.sub.3, B.sub.3, C.sub.3, and D.sub.3; or A.sub.4,
B.sub.4, C.sub.4, or D.sub.4 is N;
[0126] each R.sub.n is independently selected from the group
consisting of H; methyl; ethyl; propyl; isopropyl; n-butyl;
sec-butyl; isobutyl; CH.sub.2--(CH.sub.2).sub.n1--CH.sub.3 where
n1=5-20; CH.sub.2--(CH.sub.2).sub.n2--CH.sub.2--X where n2=0-20;
--CH.sub.2(CO)--(CH.sub.2).sub.n3--CH.sub.2--X where n3=0-20;
--CH.sub.2--Ar--X; (CH.sub.2).sub.n--X; (CH.sub.2).sub.mAr--X;
(CH.sub.2).sub.mAr--Y; (CH.sub.2).sub.n--Y; CH.sub.2CONH--Y;
CH.sub.2COO--Y; CH.sub.2CO(CH.sub.2).sub.P--Y;
(OCH.sub.2CH.sub.2).sub.m--Y; (OCH.sub.2CH.sub.2).sub.m--X;
Y.sub.2--X;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3 and
--CH.sub.2CO.sub.2CH.sub.2CH.sub.3; alkyl;
CH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3; (CH.sub.2).sub.n--X;
(CH.sub.2).sub.n--Y; (CH.sub.2).sub.nAr--X; (CH.sub.2).sub.nAr--Y;
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.3;
CH.sub.2CO.sub.2CH.sub.2CH.sub.3; (OCH.sub.2CH.sub.2).sub.m--X;
(OCH.sub.2CH.sub.2).sub.m--Y; Y.sub.2--X; o
Y.sub.2C(Z.sub.1).sub.3; Z.sub.1 is
CH.sub.2OCH.sub.2(CH.sub.2).sub.nX,
CH.sub.2OCH.sub.2(CH.sub.2).sub.nY, or
(CH.sub.2).sub.nC(O)Y.sub.2C(Z.sub.2).sub.3; Z.sub.2 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.4).sub.3; Z.sub.4 is
CH.sub.2OCH.sub.2CH.sub.2X or
(CH.sub.2).sub.nC(O)--Y.sub.2--C(Z.sub.5).sub.3; Z.sub.5 is
CH.sub.2OCH.sub.2CH.sub.2C(O)Y.sub.2C(Z.sub.6).sub.3; Z.sub.6 is
CH.sub.2OCH.sub.2CH.sub.2C(O)O(CH.sub.2CH.sub.2O).sub.mCH.sub.2CH.sub.2O.-
sup.-, (CH.sub.2).sub.nOCH.sub.2C(CH.sub.2OH).sub.3,
(CH.sub.2).sub.nOCH.sub.2CH(CH.sub.2OH).sub.2,
(CH).sub.nOCH.sub.2C(CH.sub.2OH).sub.2(CH.sub.3),
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2OH).sub.3].sub.3,
(CH.sub.2).sub.nOCH.sub.2C[CH.sub.2OCH.sub.2C(CH.sub.2O[CH.sub.2CH.sub.2O-
].sub.mCH.sub.2CH.sub.2OX).sub.3, CH.sub.2CONH--Y, CH.sub.2CO--Y,
or CH.sub.2CO(CH.sub.2).sub.P--Y; Y is OH,
(O--CH.sub.2CH.sub.2).sub.m--W.sub.1 or
(CH.sub.2CH.sub.2).sub.m--W.sub.2; W.sub.1 is OH, or
(O--(CH.sub.2CH.sub.2).sub.mOH); W.sub.2 is OR.sub.16 and R.sub.16
is alkyl; and Y.sub.2 is --(CH.sub.2).sub.nO--,
--(CH.sub.2).sub.nNH--, --(CH).sub.nS--; CH.sub.2CONH--,
CH.sub.2COO--, or CH.sub.2CO(CH.sub.2).sub.p--; and where
[0127] Ar is substituted or unsubstituted phenyl, substituted or
unsubstituted biphenyl, or substituted or unsubstituted naphthyl
and when Ar is the phenyl in --CH.sub.2--Ar--X,
(CH.sub.2).sub.mAr--X, or (CH.sub.2).sub.mAr--Y, the X or Y is
attached ortho-meta- or para to the --CH.sub.2-- attached to
pyridoporphyrazine;
[0128] n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH,
COO(alkyl.sub.1), CONH.sub.2, CONH(alkyl.sub.1),
CON(alkyl.sub.1).sub.2, CO(CH.sub.2).sub.palkyl.sub.1,
OPO.sub.3H.sub.2, PO.sub.3H.sub.2, SO.sub.3H, NH.sub.2,
N(alkyl.sub.1).sub.2, or N(alkyl.sub.1).sub.3.sup.+, where
alkyl.sub.1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
or octyl; and
[0129] L.sub.1 and L.sub.2 are, independently absent, halide, oxo,
aquo, hydroxo, CN, OPO.sub.3H, or alcohol.
[0130] 17. The kit of any one or more of embodiments 12-16, wherein
the ClO.sub.2.sup.- is provided from at least one substance
selected from the group consisting of chlorite salts.
[0131] 18. The kit of any one or more of embodiments 12-17, wherein
the ClO.sub.2.sup.- is provided from at least one substance
selected from the group consisting of sodium chlorite, potassium
chlorite, calcium chlorite and magnesium chlorite.
[0132] 19. The kit of any one or more of embodiments 12-18, wherein
the ClO.sub.2.sup.- is mixed with a solid filler.
[0133] 20. The kit of any one or more of embodiments 12-19, wherein
the ClO.sub.2.sup.- is adsorbed on at least one substance selected
from the group consisting of clay, silica, alumina and organic
polymers.
[0134] 21. The kit of any one or more of embodiments 12-20, wherein
at least one of the manganese porphyrin catalyst or a manganese
porphyrazine catalyst is adsorbed on a solid support.
[0135] 22. The kit of any one or more of embodiments 12-21, wherein
the solid support includes a substance selected from the group
consisting of clay, silica, alumina, glass beads, functionalized
polystyrene or organic polymers.
[0136] Additional embodiments include those formed by reading any
dependent claim in the claim listing below as being dependent on
any one or more preceding claim up to and including its base
independent claim.
[0137] Further additional embodiments include those formed by
supplementing any single embodiment herein or replacing an element
in any single embodiment herein with one or more element from any
one or more other embodiment herein.
EXAMPLES
[0138] The following non-limiting examples are provided to
illustrate particular embodiments. The embodiments throughout may
be supplemented with one or more detail from any one or more
example below. Still further embodiments include a method utilizing
any manganese porphyrin or manganese porphyrazine herein under any
one experimental condition described in the following examples, or
utilizing any manganese porphyrin or manganese porphyrazine herein
under any one experimental condition that can be inferred based on
those described in the following examples.
[0139] The embodiments throughout may be supplemented with one or
more detail from one or more example below, and/or one or more
element from an embodiment may be substituted with one or more
detail from one or more example below.
Example 1
[0140] Aliquots of ClO.sub.2.sup.- and Mn.sup.IIITDMImP stock
solutions were added to 10 mL 100 mM buffer in a test tube with
side arm and immediately sealed using a rubber stopper outfitted
with a fritted sparging tube. The reaction mixture was sparged with
He during the course of the reaction through another fritted
bubbler into a second test tube containing 20-40 mL of aqueous 200
mM KI. The reaction was allowed to run for 20 minutes, at which
point the trapping solution was transferred to an Erlenmeyer flask
and titrated with 0.05 M sodium thiosulfate to a colorless endpoint
(using a starch indicator). To the colorless solution,
approximately 5 mL of concentrated H.sub.2SO.sub.4 was added to
liberate more I.sub.2. This solution was titrated again. The number
of moles of ClO.sub.2 transferred during the sparging was
determined by dividing the number of moles of thiosulfate used in
the second titration by 4. By subtracting the number of moles of
ClO.sub.2 calculated from the number of moles of thiosulfate used
in the first titration and diving the total number by 2, the number
of moles of Cl.sub.2 transferred was determined.
Example 2
[0141] Heterogeneous catalysis on clay support. Mn(III)TDMImP was
supported on montmorillonite KSF by adding 1 mL of 2.5 mM MnTDMImP
to a stirring, aqueous suspension of montmorillonite (.about.200
mg/mL). Immediately the clay adsorbed the cationic porphyrin, and
the supernatant had no color when the porphyrin-clay suspension was
allowed to settle. Using the clay-bound MnTDMImP, catalyst-free
solutions of ClO.sub.2 could be prepared by stirring unbuffered
solutions of NaClO.sub.2 with aliquots of the MnTDMImP/clay slurry
in an open reaction vial, followed by filtration through
Celite/glass wool in a Pasteur pipet to remove the catalyst. Using
2 mg of the monified clay, a 5.5 mM solution of NaClO.sub.2
produced 1 mM ClO.sub.2 solution in 15 minutes (by UV-Vis
analysis). With larger amounts of the MnTDMImP/clay (10-100 mg),
the reaction was complete in less than 10 minutes, producing a
catalyst-free 2.1 mM ClO.sub.2 solution from a 9.5 mM solution of
NaClO.sub.2.
Example 3
[0142] Methyl Orange Test. In order to indirectly test for the
generation of hypochlorite (ClO.sup.-) during turnover, methyl
orange (MO, 4-dimethylaminoazobenzene-4'-sulfonic acid sodium salt)
was added to the reaction of chlorite (ClO.sub.2.sup.-) and
MnTDMImP at pH 4.7. MO reacts with chlorinating oxidants such as
ClO.sup.-, producing dichlorodimethylaniline (DDA). DDA can be
extracted from the aqueous medium with heptane and observed by
GC-MS (m/z=188).
[0143] As controls, the reactions of MO with chlorite
ClO.sub.2.sup.-, ClO.sup.-, and chlorine dioxide (ClO.sub.2) were
tested. ClO.sub.2.sup.- did not react at all with methyl orange at
pH 4.7, whereas the other two oxidants quickly bleached the methyl
orange chromophore (464 nm). ClO.sup.- produced
dichlorodimethylaniline (DDA), detectable by GC-MS. No DDA was ever
observed in reactions of MO with ClO.sub.2. Referring to FIG. 4,
however, it was observed that ClO.sub.2 quickly oxidized away
authentic DDA to unknown products. The absence of DDA observable in
reactions of MO and ClO.sub.2 does not prove that DDA is not
transiently produced.
[0144] Referring to FIG. 5, when MO was present in a solution of
MnTDMImP prior to the addition of ClO.sub.2.sup.-, a very small
amount DDA (ca. 2 .mu.mol) could be observed by GC-MS in heptane
extracts of the reaction medium (1 mM ClO.sub.2.sup.-, 1 mol %
catalyst, 100 .mu.mol MO). When MO was added to the catalytic
reaction after 1 and 5 minutes of reaction, less DDA was observed.
Because DDA is consumed by ClO.sub.2 which is being generated
during turnover, heptane extraction of the reaction mixture was
done 1 minute after MO was added. Further, when MO was added to
completed reactions of MnTDMImP/ClO.sub.2.sup.- (reaction
time=10-30 min), no DDA was observed. This qualitative experiment
therefore asserts that a species capable of chlorinating MO is
produced during turnover. Given the above controls and our proposed
mechanism, we assert that this chlorinating species is
ClO.sup.-.
Example 4
[0145] Quantifying ClO.sub.2 by Iodometry. At neutral pH, both
ClO.sub.2 and Cl.sub.2 will react with iodide (I.sup.-) to produce
iodine (I.sub.2) (Reactions 1 and 2).
ClO.sub.2+KI.fwdarw.KClO.sub.2+1/2I.sub.2 (1)
Cl.sub.2+2KI.fwdarw.I.sub.2+2KCl (2)
In addition, in the presence of H.sub.2SO.sub.4, the KClO.sub.2
produced in Reaction 1 above will further oxidize 2 I.sup.- to
I.sub.2.
KClO.sub.2+2H.sub.2SO.sub.4+4I.sup.-.fwdarw.KCl+2K.sub.2SO.sub.4+2I.sub.-
2+2H.sub.2O (3)
By sparging the reaction vessel of ClO.sub.2.sup.- and MnTDMImP
with helium into a concentrated I.sup.- solution, I.sub.2 was
produced (Reactions 1 and 2), which was titrated to a colorless
endpoint with sodium thiosulfate, after which the solution is
acidified with H.sub.2SO.sub.4 (Reaction 3) and re-titrated to a
second colorless endpoint. From these two titrations, the effective
amounts of both ClO.sub.2 and Cl.sub.2 produced and isolated from
the catalytic decomposition of NaClO.sub.2 can be determined.
Example 5
Synthesis
Synthesis and Characterization of Cationic Manganese and Iron
Porphyrazines. Tetrapyridinoporphyrazine (PyPz)
[0146] Water soluble cationic manganese tetrapyridinoporphyrazines
were prepared using a modification of Wohrle's method. Anhydrous
manganese acetate was allowed to react with either 2,3- or
3,4-dicyanopyridine in a salt bath at 200.degree. C. The green
colored crude manganese tetrapyridinoporphyrazines (MnPyPpz) were
precipitated with hexanes and then extracted with DMF to afford
blue pure Mnpypz. Both Mn(2,3-pypz) and Mn(3,4-pypz) have four
isomers each. Methylation was performed using dimethylsulphate in
DMF yielding the cationic manganese tetrapyridinoporphyrazines as
the methylsulfate salt (FIG. 7). The iron complexes have also been
synthesized.
Aetato(2,3-pyridinoporphyrazinato)manganese(III) (Compound 1)
[0147] 2,3-Dicyanopyridine (0.50 g, 3.9 mmol) and manganese acetate
(0.17 g, 0.98 mmol) were dissolved in 1-chloronaphthalene (50 mL)
and heated for 12 h at 200.degree. C. Acetone (250 mL) was added to
the cooled reaction mixture. The dark green product was filtered,
washed with acetone and dried. Yield: 0.55 g (90%). Alternate
method, 2,3-dicyanopyridine (0.50 g, 3.9 mmol) and manganese
acetate (0.17 g, 0.98 mmol) were placed in a 4-mL vial and heated
at 200.degree. C. for 4 h. The deep blue product was washed with
acetone and dried. Yield: 0.59 g (95%).
Acetato(N,N',N'',N'''-tetramethyltetra-2,3
pyridinoporphyrazinato)manganese(III) methylsulfate (Compound
2)
[0148] Compound 1 (0.25 g, 0.40 mmol) was suspended in dry NMP (or
DMF) (50 mL) and dimethyl sulfate (3.8 mL, 40 mmol) was added. The
mixture was heated at 120.degree. C. with stirring under argon for
12 h. Acetone (250 mL) was added to the cooled reaction mixture.
The dark purple product was filtered, washed with acetone and
dried. Yield: 0.385 g (85%).
Chloro(2,3-pyridinoporphyrazinato)iron(III) (Compound 3)
[0149] 2,3-Dicyanopyridine (0.50 g, 3.9 mmol) and iron(II) chloride
hydrate (0.20 g, 1.0 mmol) were placed in a 4-mL vial and heated at
200.degree. C. for 4 h. The deep green product was washed with
acetone and dried. Yield: 0.58 g (95%).
Chloro(N,N',N'',N'''-tetramethyltetra-2,3
pyridinoporphyrazinato)iron(III) methylsulfate (Compound 4)
[0150] Compound 3 (0.25 g, 0.41 mmol) was suspended in dry DMF (or
NMP) (50 mL) and dimethyl sulfate (3.8 mL, 40 mmol) was added. The
mixture was heated at 120.degree. C. with stirring under argon for
12 h. Acetone (250 mL) was added to the cooled reaction mixture.
The dark purple product was filtered, washed with acetone and
dried. Yield: 0.400 g (88%).
PF.sub.6 Salts of Compounds 2 and 4
[0151] The PF.sub.6 salts of compound 2 and 4 were synthesized by
anion exchange. Compound 2 (or 4) (0.20 mmol) was dissolved in
H.sub.2O (10 mL) and added to a solution of NH.sub.4PF.sub.6 (0.75
g, 4.7 mmol) in H.sub.2O (10 mL). The precipitate was filtered,
washed with H.sub.2O and dried. The yield was quantitative for both
manganese and iron.
3,4 isomers of compounds 2 and 4
[0152] The 3,4 isomers of compounds 2 and 4 were synthesized by
using 3,4-dicyanopyridine instead of 2,3-dicyanopyridine. The
overall yield of the manganese isomer was lower at 55%. Moreover,
this complex was very sensitive and decomposed quickly even at low
pH. The overall yield of the iron 3,4-isomer was similar to the
iron 2,3-isomer at 82%.
[0153] The compounds were tested as oxidation catalysts and
promoters.
Oxidation of Bromide
[0154] Oxone (200 .mu.M) was added to Mn(TM-2,3-PyPc) (20 .mu.M),
NaBr (10 mM) in acetate buffer (pH=4.9) in a cuvette. The UV-vis
spectrum showed the presence of Br3-. Phenol Red (50 .mu.M) was
added to the cuvette. The UV-vis spectrum indicated bromination of
the phenol red to bromophenol blue. When H.sub.2O.sub.2 (2 mM) was
used as the oxidant, bromophenol blue was also produced as
indicated by the UV-vis spectroscopy.
Oxidation of Chloride
[0155] Oxone (200 .mu.M) was added to Mn(TM-2,3-PyPc) (20 .mu.M),
NaCl (200 mM) in acetate buffer (pH=4.9) in a testtube. The tube
was shaken for 15 s and then methyl orange (200 .mu.M) was added to
the testtube and the tube was shaken for 1 min. Hexanes was added
to extract the organic soluble molecules and GC-MS indicated the
presence of mono- and dichloroaniline.
Epoxidation of CBZ
[0156] Oxone (300 nmol) was added to Mn(TM-2,3-PyPc) (50 nmol), CBZ
(200 mmol) in acetate buffer (pH=4.9) in a testtube. By HPLC
analysis, CBZ oxide was produced.
Octakis[(bismethyl)imidazoliumyl]tetraazaprophyrin[H.sub.2(Me.sub.2-Im).su-
b.8TAP].sup.8+
[0157] The synthesis of
octakis[(bismethyl)imidazoliumyl]tetraazaprophyrin will be
performed in a similar fashion to the synthesis of Barrett and
Hoffman's octacationic pyridium substituted tetraazaporphyrin (FIG.
8). Barrett and Hoffman first synthesized
2,3-bis(4-pyridyl-2,3-dicyanomaleonitrile from oxidative
dimerization of 4-pyridylacetonitrile hydrochloride. Since no
commercial sources of (1-methyl-1H-imidazol-2-yl)acetonitrile are
available, this compound was prepared by a procedure by Reese (FIG.
9). 1-Methylimidazole was allowed to react with excess
paraformaldehyde at 160.degree. C. to yield
(1-methylimidazol-2-yl)methanol. The methanol complex was then
allowed to react with thionyl chloride at reflux to give
2-(chloromethyl)-1-methylimidazole hydrochloride. Sodium cyanide
was then allowed to react with this chloro complex to yield
1-methylimidazol-2-yl-acetonitrile. With
1-methylimidazol-2-yl-acetonitrile synthesized, following Barrett
and Hoffman's procedure, the manganese
octakis[(bismethyl)imidazoliumyl]tetraazaprophyrin should be able
to be synthesized (FIG. 10).
Example 6
[0158] Proposed Mechanism I. Referring to FIGS. 2A-2B, a time
resolved ITV-vis spectra of ClO.sub.2.sup.- (359 nm) generation
when 10 .mu.M MnTDMImP (445 nm) is mixed with 1.9 mM NaClO.sub.2
(260 nm) at pH 4.7 (100 mM acetate buffer) and T=25.degree. C. The
reaction time shown is 240 s, scanning every 10 s. As shown, upon
mixing freshly prepared sodium chlorite solutions with MnTDMImP, a
large and immediate increase in the UV absorbance at 359 nm signals
the formation of ClO.sub.2. The appearance of ClO.sub.2 occurred
within seconds, concurrent with a complete decrease in the
ClO.sub.2.sup.- absorbance at 260 nm. The acid-catalyzed
disproportionation of ClO.sub.2.sup.- is sluggish above pH 3-4 and
was insignificant on the time-scales studied here. During the
initial burst of reaction, .about.50 equiv of ClO.sub.2 were
quickly generated from 190 equiv of ClO.sub.2.sup.-.
O.sub.2-evolution, as monitored using a Clark electrode, was
insignificant (<2%) The only porphyrin species observed in
solution during turnover was the starting Mn.sup.III catalyst, as
evidenced by the unshifted and undiminished Soret band at 445 nm.
Significantly, the process also proceeded efficiently when the
catalyst was adsorbed on montmorillonite clay.
[0159] The manganese porphyrin-catalyzed appearance of ClO.sub.2
was observed from pH 4.7-6.8 over the temperature range
5-35.degree. C. When ClO.sub.2.sup.- was mixed rapidly with
MnTDMImP (0.5 mol %) the observed concentration of ClO.sub.2
produced reached a plateau within two minutes (FIG. 2B). Initial
turnover frequencies at 25.degree. C. for 2 mM ClO.sub.2.sup.- and
10 .mu.M catalyst were 1.00, 1.03, and 0.47 s.sup.-1 at pH 4.7,
5.7, and 6.8, respectively, but these bulk values could be
underestimates. The maximum amount of ClO.sub.2 achieved was not
temperature dependent.
[0160] The hypochlorite ion produced in the initial step would also
be expected to oxidize Mn.sup.IIITDMImP as shown in Scheme 1. This
stoichiometry predicts that five equiv of ClO.sub.2.sup.- would be
dismutated to 4 equiv of ClO.sub.2 and 1 equiv of C.sub.1.sup.- in
this process. The observed unchanged oxidation state of the
catalyst during turnover (FIG. 1) requires that any change in the
Mn.sup.III porphyrin oxidation state be slow relative to
Mn.sup.III-regenerating reactions. As ClO.sup.- is a fast oxidant
of Mn.sup.III, the oxidation of Mn.sup.IIIby ClO.sub.2.sup.- may be
the rate-determining step of the overall catalytic cycle. At
neutral pH, the calculated reduction potentials for the
oxoMn.sup.V/Mn.sup.III couple are lowest for TDMImP. Therefore, the
imidazolium porphyrin should be oxidized most readily by
ClO.sub.2.sup.-, which is consistent with oxo-transfer from
ClO.sub.2.sup.- being the RDS. At higher pH (where no ClO.sub.2
generation was observed), ClO.sub.2.sup.- should be strong enough
to oxidize Mn.sup.III fully to Mn.sup.V based on the predicted
energetics of both species. At pH 8.0 the reaction of
ClO.sub.2.sup.- and Mn.sup.IIITDMImP produced the O.dbd.Mn.sup.IV
porphyrin, characterized by its broadened and slightly blue-shifted
Soret. Presumably, ClO.sub.2.sup.- oxidizes Mn.sup.III to
oxoMn.sup.V, which is quickly reduced by another ClO.sub.2.sup.- to
oxoMn.sup.IV. The catalytic cycle in Scheme 1 would then stall at
the Mn.sup.IV oxidation state because the O.dbd.Mn.sup.IV compound
cannot efficiently oxidize ClO.sub.2.sup.- and return to the
resting Mn.sup.III state at this pH.
[0161] ClO.sub.2 gas generated from the catalytic decomposition of
ClO.sub.2.sup.- was removed via efficient sparging of a reaction
vessel charged with pH 6.8 phosphate buffer, ClO.sub.2.sup.-, and
the catalyst. This effluent was bubbled through chilled, distilled
water, which took on the characteristic color of dilute aqueous
ClO.sub.2 and could be confirmed by UV-Vis spectroscopy. The
ClO.sub.2 collected in this way was trapped and titrated with added
iodide. Iodide is readily oxidized to I.sub.2 by ClO.sub.2, which
could then be quantified by titrimetry. Using this procedure, 46.6
.mu.moles of ClO.sub.2 were recovered from a 25.degree. C. reaction
of 98.4 .mu.moles of NaClO.sub.2 with 10 .mu.M MnTDMImP (reaction
volume 10 mL) at pH 6.8 (60% yield, .about.500 turnovers). A small
amount of iodide oxidation attributable to Cl.sub.2 (3.7 .mu.mol)
was also observed.
[0162] The various reactions of ClO.sub.2.sup.- with
metalloporphyrins reported to date are highly diverse in terms of
intermediates and products. Accordingly, it is instructive to
compare the reactivity of manganese porphyrin or phorphyrazine
catalyst systems with that of other systems, both enzymatic and
synthetic. Most notably, a water-soluble synthetic iron porphyrin
that generates O.sub.2 from ClO.sub.2.sup.- has been reported as a
biomimic of the heme protein Cld. However, two other iron
porphyrins were shown to dismutate ClO.sub.2.sup.- directly to
chlorate (ClO.sub.3.sup.-) and chloride (C.sub.1.sup.-) with no
observation of O.sub.2. Collman and Brauman, who used
ClO.sub.2.sup.- with a synthetic manganese porphyrin catalyst in
oxidations of cyclohexane, also observed O.sub.2 evolution in
non-aqueous media. The heme-thiolate enzyme chloroperoxidase
transiently generates ClO.sub.2 from ClO.sub.2.sup.-, ultimately
producing a mixture of ClO.sub.3.sup.-, Cl.sup.-, and O.sub.2 via
undetermined mechanisms. By contrast, a recent mechanistic study of
ClO.sub.2.sup.- decomposition by horseradish peroxidase (HRP) has
shown that ClO.sub.2.sup.- acts as both oxidant and reducing agent
in a peroxidase cycle that generates ClO.sub.2, but not
ClO.sub.3.sup.-. The present embodiments represents the only known
generation of ClO.sub.2 from a synthetic porphyrin system.
[0163] The proposed mechanism for ClO.sub.2.sup.- generation by
manganese porphyrin or phorphyrazine is intriguing for its
pronounced differences with a proposed mechanism for Cld and the
iron porphyrin Cld-mimics. In Cld, the Cld-mimic Fe porphyrin, and
MnTDMImP, ClO.sub.2.sup.- acts as a 2-electron oxo-transfer agent,
producing either an oxoiron.sup.IV porphyrin cation-radical or
dioxoMn.sup.V as well as an equivalent of ClO.sup.-. In the case of
Cld and the iron mimic, the newly formed ClO.sup.- presumably
reacts with Compound I to form an oxygen-oxygen bond, leading to
the release of O.sub.2. However, ClO.sup.- produced from the
oxidation of Mn.sup.IIITDMImP by ClO.sub.2.sup.- appears not to
react with the newly-formed dioxoMn.sup.V species, but instead
diffuses away to oxidize a second Mn.sup.III site.
[0164] It appears that dioxoMn.sup.V prefers an outer-sphere
electron transfer from ClO.sub.2.sup.- over the O--O bond-forming
inner sphere reaction with ClO.sup.-. This behavior might be
influenced by electrostatics. As low as pH 5, the core of the
catalyst exists as an anionic, trans-dioxo species
[O.dbd.Mn.sup.V.dbd.O].sup.-. The work required to bring together
two anions in an inner-sphere process could be far greater than
that necessary for an outer sphere process (where ClO.sub.2.sup.-
need only come qualitatively near the oxo species). Charge has been
shown to be a powerful mediator of porphyrin reactivity, as in the
example of olefin epoxidation by trans-dioxoMn.sup.V
porphyrins.
Example 7
[0165] Proposed Mechanism II. Referring to FIGS. 6A-C, the
MnTM-2,3-PyPz catalyst was characterized. The UV-Vis spectra of
MnTM2,3PyPz shows the characteristic porphyrazine Soret at 390 and
Q-bands of intensity equal to the Soret. Normally these Q-bands are
reported in the range 600-700 nm, but here we see 566 nm. The 800
nm absorbance is not found in Pz freebases, but similar absorbances
have been reported for metallated Pz. Reactions of ClO.sub.2.sup.-
with Mn(III)TM-2,3-PyPz were studied using UV-vis spectroscopy and
rapid mixing kinetic techniques. Solutions of Mn(III)TDMImP and
ClO.sub.2.sup.- were prepared in buffered solutions and mixed 1:1.
Final concentrations for reactions were obtained by dividing the
initial concentrations by two. Thirty minutes elapsed between
temperature setting and experiment to allow the cell holder and
mixing accessory to equilibrate to the set temperature. Aliquots of
ClO.sub.2.sup.- and Mn(III)TM-2,3-PyPz stock solutions were added
to 10 mL 100 mM buffer in a test tube with side arm and immediately
sealed using a rubber stopper outfitted with a fritted sparging
tube. The reaction mixture was sparged with He during the course of
the reaction through another fritted bubbler into a second test
tube containing 20-40 mL of aqueous 200 mM KI for determination of
total chlorine dioxide produced.
[0166] Alternatively, Mn(III)TH-2,3-PyPz was supported on
montmorillonite KSF by adding 1 mL of 2.5 mM Mn(III)TH-2,3-PyPz to
a stirring, aqueous suspension of montmorillonite (.about.200
mg/mL). Immediately the clay adsorbed the cationic porphyrin, and
the supernatant had no color when the porphyrin-clay suspension was
allowed to settle. Using the clay-bound Mn(III)TH-2,3-PyPz,
catalyst-free solutions of ClO.sub.2 could be prepared by stirring
unbuffered solutions of NaClO.sub.2 with aliquots of the
Mn(III)TH-2,3-PyPz/clay slurry in an open reaction vial, followed
by filtration through Celite/glass wool in a Pasteur pipet to
remove the catalyst. Using 2 mg of the monified clay, a 5.5 mM
solution of NaClO.sub.2 produced 1 mM ClO.sub.2 solution in 15
minutes (by UV-Vis analysis). With larger amounts of the
Mn(III)TH-2,3-PyPz/clay (10-100 mg), the reaction was complete in
less than 10 minutes, producing a catalyst-free 2.1 mM ClO.sub.2
solution from a 9.5 mM solution of NaClO.sub.2.
[0167] The electron-deficient manganese(III)
tetra-(N,N-dimethyl)imidazolium porphyrin (MnTDMImP),
tetra-(N,N-dimethyl)benzimidazolium (MnTDMBImP) porphyrin and
manganese(III) tetramethyl-2,3-pyridinium porphyrazine (MnTM23PyPz)
were found to be the most efficient catalysts for the conversion of
chlorite to chlorine dioxide at neutral pH and with mild
conditions. The more typical manganese
tetra-4-N-methylpyridiumporphyrin (Mn-4-TMPyP) was useful in the
process, but less effective than Mn-4-TMPyP. Rates for the best
catalysts were in the range of 0.24-32 TO/s with MnTM23PyPz showing
the fastest turnover. The kinetics of reactions of the various
ClO.sub.x species (e.g. chlorite ion, hypochlorous acid and
chlorine dioxide) with authentic oxomanganese(IV) and
dioxomanganese(V) MnTDMImP intermediates were studied with
stopped-flow spectroscopic methods, thus allowing independent
confirmation of the individual steps in this catalysis. The
proposed mechanism indicates a dual role for chlorite ion as both
an oxidant and the substrate precursor to ClO.sub.2. Rate-limiting
oxidation of the manganese(III) catalyst by chlorite ion via oxygen
atom transfer is proposed to afford a trans-dioxomanganese(V)
intermediate. Both trans-dioxomanganese(V)TDMImP and
oxoaqua-manganese(IV)TDMImP oxidize chlorite ion by 1-electron,
generating the product chlorine dioxide with bimolecular rate
constants of 6.30.times.10.sup.3 M.sup.-1s.sup.-1 and
3.13.times.10.sup.3 M.sup.-1 s.sup.-1, respectively, at pH 6.8.
Chlorine dioxide was able to oxidize manganese(III)TDMImP to
oxomanganese(IV) at a similar rate, establishing a redox
steady-state equilibrium under turnover conditions. Another
important oxygen transfer reaction controlling this process is the
rapid, reversible oxygen atom transfer between dioxoMn(V)TDMImP and
chloride ion. The measured equilibrium constant for this reaction
(K.sub.eq=2.2 at pH 5.1) afforded a value for the oxoMn(V)/Mn(III)
redox couple under catalytic conditions (E'=1.35 V vs NHE). In
subsequent processes, chlorine dioxide reacts with both
oxomanganese(V) and oxomanganese(IV) TDMImP to afford chlorate ion.
Kinetic simulations of the proposed mechanism using experimentally
measured rate constants were in agreement with observed chlorine
dioxide growth and decay curves, measured chlorate yields, and the
oxoMn(IV)/Mn(III) redox potential (1.03 V vs NHE). This acid-free
catalysis could form the basis for a new process to make
ClO.sub.2.
[0168] Catalytic Generation of ClO.sub.2.sup.- from
ClO.sub.2.sup.-
[0169] The cationic, water-soluble manganese porphyrins (shown
below) and a similar porphyrazine complex (also shown below)
catalyzed the rapid production of chlorine dioxide from chlorite
ion under mild conditions. The evolved ClO.sub.2 could be monitored
from the appearance of the characteristic chromophore at 359 nm
(FIGS. 11A-B). During turnover, the visible spectra of the
Mn.sup.III catalysts remained largely unchanged, demonstrating the
resistance of the catalyst to bleaching as well as providing
mechanistic insight. The initial turnover rates for each of the
studied catalysts are reported in Table 2, below. Extremely high
activity (32 TO/s) was observed for the manganese(III)
porphyrazine, MnTM23PyPz.
##STR00016##
[0170] Manganese porphyrins and porphyrazine studied as
catalysts.
TABLE-US-00002 TABLE 2 initial turnover frequency Catalyst
(s.sup.-1) mol % cat. MnTM4PyP* 0.01 0.25 MnTM2PyP* 0.24 0.25
MnTDMImP* 0.40 0.25 MnTDMBImP* 0.48 0.50 MnTM23PyPz** 32.0 0.27 *pH
6.8 50 mM phosphate buffer, T = 25.degree. C., 2.0 mM NaClO.sub.2
**pH 4.5 50 mM acetate buffer, T = 25.degree. C., 1.8 mM
NaClO.sub.2
[0171] The appearance of ClO.sub.2 using MnTDMImP was studied in
100 mM acetate buffer (pH 4.7 and 5.7) and 100 mM phosphate buffer
(pH 6.8). Initial turnover frequencies observed under these
conditions at 25.degree. C. for 2 mM ClO.sub.2.sup.- and 10 .mu.M
Mn.sup.IIITDMImP were 1.00, 1.03, and 0.42 at pH 4.7, 5.7, and 6.8,
respectively. However, the turnover frequency was influenced more
by buffer composition than by pH. Increasing buffer concentration
and ionic strength (with added sodium perchlorate) was found to
inhibit the MnTDMImP-catalyzed reaction by a factor of 5 in the
range 5 mM-100 mM while at a constant buffer concentration, the
turnover frequency did not change from pH 5.9 to 7.01.
[0172] When ClO.sub.2.sup.- was rapidly mixed with Mn.sup.IIITDMImP
at 25.degree. C., the spectroscopically-observed concentration of
ClO.sub.2 produced rose quickly and reached a plateau within 3 min.
The product ClO.sub.2 absorbance subsequently decayed in a slower
process over the course of about 15 min. The maximum ClO.sub.2
concentration was not affected by temperature (2.0 mM ClO.sub.2,10
.mu.M Mn.sup.IIITDMImP, 100 mM pH 6.8 phosphate buffer), although
the reaction rate increased markedly from 5 to 35.degree. C.
[0173] Reduction of oxoMn.sup.V and oxoMn.sup.IVTDMImP by
ClO.sub.2.sup.-
[0174] The reactions of both oxoMn.sup.VTDMImP and
oxoMn.sup.IvTDMImP with ClO.sub.2.sup.- were studied by
double-mixing, stopped-flow spectroscopy. In the first push,
authentic oxoMn.sup.V or oxoMn.sup.IV was generated by mixing
Mn.sup.IIITDMImP with 1 equiv of oxone or tBuOOH, respectively, in
10 mM pH 8.0 phosphate buffer. In the second push, oxoMn.sup.V or
oxoMn.sup.V was mixed with an excess of ClO.sub.2.sup.- in 100 mM
pH 4.7 acetate or pH 6.8 phosphate buffer. This "pH jump"
experiment permitted observation of the reaction between each of
the high-valent manganese species with ClO.sub.2.sup.- at lower pH
values.
[0175] The decay of oxoMn.sup.V (as measured by the characteristic
Soret absorbance at 425 nm) was pH-dependant and followed
pseudo-first order kinetics when mixed with an excess of
ClO.sub.2.sup.-. This decay was fit to a modeled exponential decay
curve in order to obtain the observed pseudo-first order rate
constant (k.sub.obs), which was plotted as a function of
[ClO.sub.2.sup.-]. The apparent second-order rate constants
(k.sub.app) calculated from the slope of k.sub.obs vs.
[ClO.sub.2.sup.-] are 6.8.times.10.sup.5 and 6.3.times.10.sup.3
M.sup.-1 s.sup.-1 at pH 4.7 and 6.8, respectively.
[0176] At pH 4.7, the 1-electron reduction of oxoMn.sup.V by
ClO.sub.2.sup.- was fast and allowed the direct observation of a
reduced oxoMn.sup.IVTDMImP catalyst with a single isosbestic point
between a Soret bands at 437 nm (5 .mu.M oxoMnVTDMImP and 125 .mu.M
ClO2- in 100 mM pH 4.7 acetate buffer over 0.3 s). By contrast, at
pH 6.8 the reaction of oxoMn.sup.V with ClO.sub.2.sup.- afforded
Mn.sup.III (10 .mu.M oxoMnVTDMImP and 1.0 mM ClO2- in 100 mM pH 6.8
phosphate buffer over 3 s). The presence of two time-separated
isosbestic points (436 nm and 432 nm) during this reaction
demonstrated the intermediacy of oxoMn.sup.IV in the reaction
between oxoMn.sup.V and ClO.sub.2.sup.-. Under these conditions,
the apparent second-order rate constant k.sub.app was determined by
first obtaining a pseudo-first order rate constant (k.sub.obs)
during the first phase of the reaction (where only the 436 nm
isosbestic was observed).
[0177] The reaction between oxoMn.sup.IV and an excess of
ClO.sub.2.sup.- was similarly found to result in a pseudo-first
order decay of oxoMn.sup.IV to Mn.sup.III (as measured by the
characteristic Soret absorbance of oxoMn.sup.IV at 422 nm) at pH
4.7 and 6.8 (10 .mu.M oxoMnIVTDMImP and 1.0 M ClO2- in 100 mM pH
4.7 acetate buffer over 3 s and 10 .mu.M oxoMnIVTDMImP and 1.0 M
ClO2- in 100 mM pH 6.8 phosphate buffer over 1.5 s). A single
isosbestic point was observed at 433 nm between the Soret bands of
oxoMn.sup.IV and Mn.sup.III. The apparent second-order rate
constants measured for the reduction of oxoMn.sup.IV by
ClO.sub.2.sup.- are 6.0.times.10.sup.3 and 3.1.times.10.sup.3
M.sup.-1s.sup.-1 at pH 4.7 and 6.8, respectively.
[0178] Measurement of k.sub.app for Oxo-Transfer Between HOCl and
Mn.sup.III
[0179] The reaction between hypochlorous acid (HOCl) and
Mn.sup.IIITDMImP was studied by single-mixing stopped-flow
spectrometry. At pH 6.8, the reaction resulted in complete
formation of oxoMn.sup.V in <100 ms (Mn.sup.IIIIIITDMImP with
HOCl at pH 6.8, 5.1, or 4.7; buffer conditions--pH 6.8, 100 mM
phosphate buffer; pH 4.7 and 5.1, 100 mM acetate buffer; reaction
conditions--(a) 10 .mu.M MnIII, 5 equiv HOCl; (b) 5 .mu.M
Mn.sup.III, 20 equiv HOCl; (c) 5 .mu.M Mn.sup.III, 50 equiv HOCl).
An apparent second-order rate constant for the reaction was
determined by measuring k.sub.obs of oxoMn.sup.V appearance (425
nm) as a function of [HOCl]. The calculated rate constant (k.sub.4)
at pH 6.8 was 1.7.times.10.sup.6 M.sup.-1 s.sup.-1. An initial-rate
analysis of oxoMn.sup.V formation gave a slower rate constant of
1.47.times.10.sup.5 M.sup.-1s.sup.-1.
[0180] At pH 4.7, complete formation of oxoMn.sup.V could not be
elicited with even a 50-fold excess of HOCl. Nevertheless, the
apparent second-order rate constant (k.sub.4=6.6.times.10.sup.4
M.sup.-1s.sup.-1) under these conditions was calculated from a plot
of k.sub.obs for the decrease in Mn.sup.III absorbance (444 nm)
versus [HOCl]. A similar analysis using the method of initial rates
provided a lower calculated k.sub.4=4.22.times.10.sup.3
M.sup.-1s.sup.-1. After a quick reaction time (<0.1 s at pH
4.7), the concentrations of Mn.sup.III and oxoMn.sup.V reached an
apparent steady-state equilibrium. This steady-state observation
can be better demonstrated at slightly less-acidic conditions of pH
5.1.
[0181] Reaction of ClO.sub.2 with Mn.sup.IIITDMImP
[0182] In order to account for the observed decay of ClO.sub.2
(FIG. 3), the reaction of ClO.sub.2 with Mn.sup.IIITDMImP was
investigated. The ClO.sub.2 absorbance at 360 nm quickly
disappeared in the presence of Mn.sup.IIITDMImP at pH 6.8, but not
pH 4.7 (Initial [ClO.sub.2] was 0.53 mM at pH 4.7 and 0.59 mM at pH
6.8). In both cases, the only porphyrin oxidation state observed in
solution was Mn.sup.III.
[0183] Electron Transfer Between oxoMn.sup.IV, oxoMn.sup.V and
ClO.sub.2
[0184] Stopped-flow techniques were again used to observe how
high-valent species oxoMn.sup.VTDMImP and oxoMn.sup.IVTDMImP react
with ClO.sub.2. Both oxoMn.sup.V and oxoMn.sup.IV reacted with
ClO.sub.2 via 1-electron transfers. Although oxoMn.sup.IV did not
build up in the reaction of oxoMn.sup.V with ClO.sub.2, the
observation of two, time-separated isosbestic points indicates the
intermediacy of oxoMn.sup.IV in the reaction. The product of
1-electron oxidation of ClO.sub.2 is formally a chlorine(V)
species, presumably chlorate (ClO.sub.3.sup.-). The apparent
second-order rate constants (k.sub.app) for the reduction of
oxoMn.sup.V by ClO.sub.2 were 1.6.times.10.sup.4 M.sup.-1s.sup.-1
and 2.2.times.10.sup.4 M.sup.-1s.sup.-1 at pH 6.8 and 4.7,
respectively. Calculated k.sub.app for the reduction of
oxoMn.sup.IV by ClO.sub.2 are 1.2.times.10.sup.4 M.sup.-1s.sup.-1
and 7.9.times.10.sup.3 M.sup.-1s.sup.-1 at pH 6.8 and 4.7,
respectively.
[0185] ClO.sub.3.sup.- Determination by HPLC
[0186] The observation that ClO.sub.2 itself acted as a 1-electron
reductant of oxoMn.sup.IVTDMImP and oxoMn.sup.VTDMImP suggests that
some chlorine(V) species, presumably ClO.sub.3.sup.-, was produced.
An indirect UV-detection HPLC method was therefore employed to
confirm and quantify the presence of ClO.sub.3.sup.- in reaction
mixtures of either ClO.sub.2.sup.- or ClO.sub.2 with
Mn.sup.IIITDMImP (Table 3). Buffer, catalyst, ClO.sub.2.sup.-, and
ClO.sub.2 stock solutions were free of ClO.sub.3.sup.- prior to
reaction. A measured amount of either ClO.sub.2.sup.- or ClO.sub.2
was added to solutions of MnTDMImP and stirred for ca. 1 h before
being analyzed. Because the excess buffer anions co-eluted with
chloride anion, the quantification of chloride produced by the
catalytic decomposition of ClO.sub.2.sup.- could not be
accomplished.
TABLE-US-00003 TABLE 3 [ClO.sub.3-].sub.obsd [ClO.sub.3-].sub.pred
Added substrate (mM) (mM) 1 mM ClO.sub.2 0.7 0.8 1 mM ClO.sub.2-
0.6 0.7 2 mM ClO.sub.2- 1.7 1.4
Table 3 shows the measured concentrations of ClO.sub.3.sup.-
produced ([ClO.sub.3.sup.-].sub.obsd) from the reaction of 10 .mu.M
Mn.sup.IIITDMImP with a given amount of substrate (ClO.sub.2 or
ClO.sub.2.sup.-) at pH 6.8. Also shown are the ClO.sub.3.sup.-
concentrations predicted ([ClO.sub.3.sup.-].sub.pred) by a kinetic
model of the proposed mechanism (vida infra) given the same
substrate/catalyst starting conditions.
[0187] Scheme 1, below, was proposed for the reaction
mechanism.
##STR00017##
[0188] The key initiating step in this catalytic cycle was
suggested to be oxygen atom transfer from chlorite to the
Mn.sup.III catalyst to form trans-dioxoMn.sup.VTDMImP. The
thermodynamic driving force for oxo-transfer from chlorite ion is
only slightly less than that of hypobromite ion (BrO.sup.-)
(.DELTA..DELTA.G.degree.=+16.7 kJ mol.sup.-1). Hypobromite is a
very facile oxo-transfer agent in its reaction with Mn.sup.III
porphyrins, with a rate constant for oxo-transfer from HOBr to
Mn.sup.IIITDMImP.about.10.sup.5 M.sup.-1 s.sup.-1 at neutral pH.
For the reaction with chlorite ion, the fact that the Mn.sup.III
oxidation state of the catalyst persisted during turnover requires
that any change in the porphyrin oxidation state from Mn.sup.III be
slow relative to Mn.sup.III-forming reactions. Therefore, it was
concluded that the oxidation of Mn.sup.III by ClO.sub.2.sup.- must
be the rate-determining step of the overall cycle. Accordingly, a
slower 2-electron oxidation of Mn.sup.III by ClO.sub.2.sup.-,
generating HOClO and trans-dioxoMn.sup.V is consistent with these
observations. Interestingly, the pH-independence of the turnover
rate implies that the oxygen transfer step to afford the Mn.sup.V
species is pH-independent and occurs at about the same rate as the
analogous heterolysis of HOO--Mn.sup.IIITDMImP, which also affords
Mn.sup.V.
[0189] The evolved ClO.sub.2 can be efficiently removed from the
reaction vessel via simple sparging or air stripping during
turnover. Further, the catalysts are active on a solid support,
suggesting their use in a flow system, a cartridge or a trickle-bed
reactor. Methods for greatly enhancing the rate of
ClO.sub.2-generation and the reduction of impurities such as
chlorine may be achieved by ligand tuning, or by using
externally-added oxidants to overcome the relatively slow,
chlorite-initiated oxo-transfer step.
[0190] Experimental
[0191] Reagents
[0192] Sodium chloride, sodium chlorate, t-butyl hydroperoxide (70%
aqueous solution), and Oxone were purchased from Aldrich and used
as received. Sodium chlorite was obtained from Aldrich as >80%
technical grade and recrystallized twice from ethanol/water
(>95% final). All oxidant stock solutions were prepared fresh
daily and standardized by iodometeric titration before use. Dilute
(0.5-10.0 mM) chlorite solutions were standardized
spectrophotometrically (.epsilon..sub.260 nm=154 cm.sup.-1
M.sup.-1). Buffers were prepared fresh each day using either acetic
acid/sodium acetate (pH=4.7, 5.7) or potassium phosphate
(monobasic)/potassium phosphate (dibasic) (pH=6.8, 8.0) and
pH-adjusting no more than 0.1 units using perchloric acid or sodium
hydroxide. ClO.sub.2 was prepared from ClO.sub.2.sup.- using a
previously reported procedure. Briefly, a 2.5% w/w solution of
NaClO.sub.2 was acidified with sulfuric acid under an argon flow in
the dark. The evolved gas was carried by the argon flow through a
gas scrubbing tower containing a 2.5% w/w solution of NaClO.sub.2
and bubbled through deionized water in a chilled amber bottle.
Aliquots of the resulting solution were frozen at -30.degree. C.
for prolonged storage. The concentration of ClO.sub.2 was checked
immediately prior to use (.epsilon..sub.359nm=1230 cm.sup.-1
M.sup.-1). Leftover ClO.sub.2 from all experiments was neutralized
with sodium iodide before being disposed of in general waste.
Mn.sup.IIITDMImP was synthesized as the chloride salt using
reported procedures. MnTM2PyP and MnTM4PyP were purchased from Mid
Century and purified by double precipitation. MnTM23PyPz was
prepared following the method of Wohrle. Briefly, manganese
diacetate (170 mg) and pyridine-2,3-dicarbonitrile (500 mg) were
heated in an unsealed reaction tube to 200.degree. C. with
mechanical stirring for 4 h. The deep blue solid product (a mixture
of isomers) was washed with acetone, isolated by filtration,
suspended in 50 mL DMF, and tetra-methylated using excess dimethyl
sulfate at 120.degree. C. for 12 h. Product was precipitated with
acetone and purified by double precipitation.
[0193] Instrumentation
[0194] UV-Vis spectroscopic measurements were taken using a
Hewlett-Packard 8453 diode array spectrophotometer equipped with a
temperature-controlled cell housing, VWR 1140 thermostat bath and a
Hi-Tech SFA Rapid Kinetics Accessory. Stopped-flow experiments for
fast reactions were carried out using a Hi-Tech SF-61 double-mixing
instrument with a 1 cm path length equipped with an ISOTEMP 1016 S
thermostat bath. Ion chromatography was accomplished with an HPLC
system consisting of a Waters 600 controller, Hamilton PRP X-100
column, and Waters 996 photodiode array detector.
[0195] Stopped-Flow Experiments
[0196] Reactions of ClO.sub.2.sup.- with Mn.sup.III porphyrins were
studied using traditional UV-vis and rapid mixing techniques.
Solutions of catalyst and ClO.sub.2.sup.- were prepared in buffered
solutions and mixed 1:1. All rate calculations were based on final
concentrations resulting from this dilution. The oxidations of
ClO.sub.2.sup.- and ClO.sub.2 by oxoMn.sup.VTDMImP and
oxoMn.sup.IVTDMImP were studied in double mixing mode using diode
array detection. Solutions of Mn.sup.IIITDMImP and oxidant (oxone,
tBuOOH) were prepared in weak pH=8.0 phosphate buffer (10 mM) and
mixed 1:1 in a first push. After a short aging time to ensure
complete conversion to the high-valent species (2-150 s, fine tuned
for each experiment), the porphyrin solution was mixed 1:1 with the
substrate (ClO.sub.2.sup.- or ClO.sub.2) prepared in a higher
strength buffer (100 mM) at the pH to be studied (4.7 or 6.8). All
concentrations used in subsequent rate calculations accounted for
the 4-fold and two-fold dilutions inherent to the double-mixing
technique. Each reaction was run in duplicate or triplicate at
T=25.degree. C. Averaging of the runs and analysis of the data was
accomplished using the KinetAsyst 3 software package. Kinetic
simulations of the overall mechanism were performed with the
Berkeley-Madonna software package.
[0197] Ion Chromatography Experiments
[0198] Aliquots of ClO.sub.2.sup.- or ClO.sub.2 solutions were
added to buffered solutions of Mn.sup.IIITDMImP under mechanical
stirring at ambient temperatures. ClO.sub.3.sup.- was quantified
using an indirect ion chromatography method. In brief, an aqueous
solution of 4-aminosalicylic acid (4 mM) was pH adjusted to pH=6.0
and employed as the mobile phase. Reaction samples were injected
directly without any modification. The eluent was monitored at 320
nm, and a decrease in absorbance was observed as anions were
eluted. Concentration of analyte was calculated directly from total
area of the peak using a concentration curve prepared daily using
prepared standards.
Example 8
Manganese Catalyzed Process for the Oxidation of Aqueous
Cyanide
[0199] It was discovered that the presence of cyanide accelerated
chlorite depletion by manganese porphyrin catalysts; in particular,
Mn(TM-2-PyP). Surprisingly, none of the expected ClO.sub.2 product
was observed. Motivated by this finding, the experiments described
below aimed to determine the fate of ClO.sub.2 and revealed that it
is indeed formed. Once generated, ClO.sub.2 immediately reacts with
cyanide, forming cyanogen or cyanate and in the process
regenerating chlorite. Thus, the chlorite starting material may be
recycled many times. The cyanide oxidation products, cyanate and
cyanogen, are ultimately hydrolyzed to two less toxic products,
CO.sub.2 and oxalic acid. This rapid catalysis forms the basis for
a new cyanide detoxification process, and the methods,
compositions, and kits involving it are embodiments herein.
[0200] The presence of cyanide was found to significantly
accelerate the depletion of chlorite by a manganese porphyrin
complex, Mn(TM-2-PyP). However, no ClO.sub.2 product was observed,
prompting the further investigation in the present work. It was
hypothesized that: (1) the catalyst was still producing ClO.sub.2
from chlorite, but that (2) as soon as ClO.sub.2 product formed, it
reacted with cyanide by one or both of the following reactions to
detoxify cyanide using ClO.sub.2:
CN.sup.-+2ClO.sub.2(g)+2OH.sup.-.fwdarw.CNO.sup.-+2ClO.sub.2.sup.-+H.sub-
.2O (1)
ClO.sub.2+CN.sup.-.fwdarw.ClO.sub.2.sup.-+.CN (2)
[0201] Under this hypothesis, the MnPor/chlorite reaction could be
a novel in-situ method to detoxify cyanide.
[0202] These experiments had the aim to determine: (1) whether the
Mn(TM-2-PyP) catalyst produces ClO.sub.2 from chlorite in the
presence of cyanide, and (2) if so, what is the fate of ClO.sub.2.
It was hypothesized that ClO.sub.2 was still produced catalytically
under these conditions, but that it immediately reacts with
CN.sup.-, perhaps by Equations (1) and (2). In order to test this
hypothesis, two specific aims were devised: [0203] 1. Compare the
products of CN.sup.- when reacted with either:
authentically-prepared ClO.sub.2 ("control experiment") or
Mn(TM-2-PyP) catalyst in the presence of chlorite ("catalytic
experiment"). [0204] 2. Propose a reaction pathway to describe the
MnPor/chlorite reaction as modified by the presence of cyanide.
[0205] The Experimental Approach was as follows: [0206] 1.
.sup.13CN.sup.- was reacted with either: (1) equimolar ClO.sub.2
gas (control experiment) or (2) equimolar chlorite in the presence
of a catalytic amount of Mn(TM-2-PyP) (catalytic experiment). The
distribution of the products of cyanide oxidation by the two
ClO.sub.2-generation methods were identified by quantitative
.sup.13C NMR spec-troscopy and compared. [0207] 2. Based on the
distribution of cyanide oxidation products and the known reactions
for their formation, a pathway for the MnPor/chlorite/cyanide
reaction is proposed below.
[0208] To test whether ClO.sub.2 generated from chlorite a
manganese porphyrin would react with in-situ with cyanide in the
same way as authentically-generated ClO.sub.2, .sup.13C-labeled
KCN.sub.2was reacted with either .apprxeq.1 equivalent of authentic
ClO.sub.2 (control experiment) or one equivalent of ClO.sub.2.sup.-
in the presence of 5 .mu.M Mn(TM-2-PyP) (catalytic experiment).
These two reaction vials were monitored by UV/Vis spectroscopy for
ten minutes. Then, both one hour later and 15 days later, the
quantitative .sup.13C NMR spectra were obtained.
[0209] In the control experiment, the reaction between authentic
ClO.sub.2.sup.- and cyanide formed chlorite (ClO.sup.-) and a
distribution of cyanide oxidation products. The formation of
chlorite was confirmed by UV/Vis, and the cyanide oxidation
products were identified by quantitative 1.sup.3C NMR
spectroscopy.
[0210] Chlorite Product.
[0211] To determine how many equivalents of cyanide were required
to react fully with 1 equiv ClO.sub.2, the titration shown in FIG.
12 was performed. Referring to this figure, 1.4 equivalents of
cyanide were necessary to generate chlorite from ClO.sub.2 in 100%
yield (blue trace). Thus, in the "control experiment,"
.sup.13CN.sup.- and ClO.sub.2 were reacted in a 1.4:1 ratio,
producing 1 equiv chlorite and cyanide oxidation products as
analyzed by NMR spectroscopy.
[0212] Cyanide Oxidation Products.
[0213] Both one hour and 15 days after the initial reaction between
.sup.13CN.sup.- and ClO.sub.2, quantitative .sup.13C NMR
spectroscopy was used to assess the fate of cyanide. After one
hour, the major products were 1-cyanoformamide (62%), HCN (18%),
and cyanate (15%). However, after 15 days, the only species
observed were oxalic acid (75%) and carbon dioxide (25%).
[0214] Catalytic Experiments.
[0215] In the catalytic experiment, 5 .mu.M Mn(TM-2-PyP) was
reacted with 40 mM chlorite in the presence of 40 mM
.sup.13CN.sup.-. As shown in the UV/Vis spectrum in, chlorite was
rapidly depleted but no ClO.sub.2 was observed. An hour after the
initial reaction, quantitative .sup.13C NMR spectroscopy was used
to assess the fate of cyanide. The major products were cyanate
(34%) and oxalic acid (37%), with small amounts of cyanogen (9%),
CO.sub.2 (5%), 1-cyanoformamide (5%), and HCN (3%).
[0216] Comparison of Cyanide Oxidation Products
[0217] In both experiments, ClO.sub.2 oxidized cyanide to two
initially observed products: the one-carbon product cyanate
(OCN.sup.-) and the two-carbon product cyanogen (N--C--C--N)
through a fast C--C bond-forming radical pathway described below.
These products were eventually observed to hydrolyze to carbon
dioxide (CO.sub.2) and oxalic acid, respectively.
[0218] A key result from this study is that the product
distributions of cyanide oxidation products were highly similar for
the control and the catalytic experiment. The partitioning into the
two initial products was roughly 1:1.8 cyanate:cyanogen for the
control, and 1:1.1 for the catalytic experiment.
[0219] This similarity suggests that ClO.sub.2 oxidized CN.sup.- in
both cases. Therefore, in the catalytic experiment, ClO.sub.2 was
formed within minutes. It can be reasonably stated that there are
only two chemical reactions that could be forming ClO.sub.2: the
MnPor/chlorite reaction, and the OCN.sup.-/ClO reaction described
in Equation (1), which could occur since cyanate is formed.
However, the OCN.sup.-/ClO.sup.- reaction was found to be
exceedingly slow (<1% conversion in ten minutes), as described
in the Materials and Methods section, below. Thus, the .sup.13C NMR
results verify that in the presence of cyanide, Mn(TM-2-PyP) is
still transforming chlorite into ClO.sub.2. The product ClO.sub.2
is not observed by UV/Vis because it uickly oxidizes cyanide to
less toxic forms (e.g. cyanate, oxalic acid, CO.sub.2).
[0220] Observations of the two immediate cyanide oxidation
products, cyanate and cyanogen, are briefly discussed.
[0221] Cyanate and Hydrolysis to CO.sub.2.
[0222] In both the control and catalytic experiments, cyanide was
oxidized to cyanate, as directly observed by .sup.13C NMR after an
hour. Cyanate is assigned to the 1:1:1 triplet at 128.69 ppm. This
signal was verified by an authentic cyanate spectrum shown in FIG.
13. This figure illustrates .sup.13CNMR spectrum of the cyanate
anion in 10:90 H.sub.2O:D.sub.2O. The 1:1:1 triplet indicates
.sup.13C-.sup.14N coupling. This result was surprising; coupling to
nitrogen is not usually observed because quadrupolar nuclei such as
nitrogen (I=1) have very fast relaxation times, so that the
polarization of N relaxes too fast to be detected when the
excitation of .sup.13C is measured. However, it has been observed
that axially symmetric molecules with very short correlation times
can exhibit C--N coupling in polar solvents. Aqueous cyanate may be
such an instance.
[0223] Finally, cyanate is known to hydrolyze to carbon dioxide and
NH.sub.3/NH.sup.+, as shown in FIG. 14. Referring to this figure,
it was observed that CO.sub.2 was the hydrolysis product of cyanate
anion. CO.sub.2 was observed after an hour in the catalytic
experiment and as an ultimate product in the authentic ClO.sub.2
control experiment.
[0224] Cyanogen and Hydrolysis to 1-Cyanoformamide and Oxalic
Acid.
[0225] In both experiments, some cyanide was oxidized to the highly
reactive cyanogen radical, C--N. This species quickly forms the
dimer compound N--C--C--N, termed cyanogen in the literature.
[0226] Two common products of cyanogen hydrolysis are oxalic acid
and 1-cyanoformamide. The structures of these products are
illustrated on FIG. 15. The presence of oxalic acid in both
reaction mixtures at 160 ppm was confirmed by comparison with a
reference signal. However, no reference .sup.13C NMR spectrum of
1-cyanoformamide could be found. This lack is curious, because this
compound has been studied for at least the past sixty years and has
been characterized by IR, micro-wave, rotational NMR, and mass
spectrometry.
[0227] It is probable that researchers have failed to characterize
1-cyanoformamide by .sup.13C NMR for toxicity or instability
reasons.
[0228] Therefore, a spectrum for 1-cyanoformamide was predicted
using the Gaussian03 computational suite, yielding two doublets,
one due to each carbon. The two carbons are in magnetically
distinct environments and each is split by the other with a
coupling constant J.sub.CC=97.2 Hz. The carbamoyl-side carbon
signal is centered at 146.66 ppm, while the cyanide-side carbon
signal is centered at 115.34 ppm. Since the latter carbon has a
magnetic environment similar to that of HCN, its chemical shift
should be expected to be similar to that of HCN. The reference peak
for HCN is at 112.49 ppm, in close agreement with the
calculation.
[0229] The signals observed experimentally in the reaction mixtures
are in good agreement with the calculated signals for
1-cyanoformamide. In the experimental spectra, the peaks appeared
at 111.5 ppm and 146.17 ppm. The integrations of the two carbon
signals had a ratio of 1:1.1. The coupling constant J.sub.CC=87.1
Hz, which is typical for C--C coupling.
[0230] Notably, 1-cyanoformamide is known to be particularly
unstable to hydrolysis by base/hydroxide in aqueous solutions. In
this work, 1-cyanoformamide was observed in considerable amount,
accounting for 62% of the cyanide oxidized by authentic ClO.sub.2.
This result may be explained by the observation in the literature
that inorganic buffers--including phosphate, which was present in
100 mM concentration in this experiment--stabilize 1-cyanoformamide
toward hydrolysis.
[0231] Overall, the .sup.13C NMR results indicated similar product
distributions for both the control and catalytic experiments. This
key result indicates that the manganese porphyrin still produces
ClO.sub.2 from chlorite in the presence of cyanide.
[0232] The motivation for this work was the observation that
catalytic chlorite depletion by Mn(TM-2-PyP) occurred much more
rapidly in the presence of cyanide and that the expected product,
ClO.sub.2, was not observed. It was hypothesized that ClO.sub.2 was
being produced catalytically, but was immediately reacting with the
excess cyanide. The experiments in this work confirmed this
hypothesis by identifying the products of cyanide oxidation.
Cyanate and cyanogen (N--C--C--N) were the immediate products, and
they were ultimately hydrolyzed to CO.sub.2 and oxalic acid,
respectively. This confirmation now enables the study of the
cyanide-modified catalytic mechanism to proceed. In addition, the
results from this work provide a framework for a potential cyanide
detoxification method, discussed below.
[0233] MnPor/Chlorite Reaction Pathway with Excess Cyanide.
[0234] A reactive pathway that uses a manganese porphyrin and
minimal chlorite to detoxify excess cyanide by recycling the
chlorite through the ClO.sub.2 intermediate is described herein.
This pathway contains each of the reactions studied individually in
this work: (1) first, the catalytic reaction to create ClO.sub.2,
(2) then, the two cyanide oxidation reactions that utilize
ClO.sub.2, and (3) finally, the two hydrolysis pathways of the
CN.sup.- oxidation products. The balanced chemical reactions of
these processes are known from the literature. Simply combining
these reactions and their stoichiometries results in the proposed
reaction pathway in Scheme 1, which occurs in the following
sequence: [0235] 1. First, five chlorite molecules are transformed
into 4ClO.sub.2 and 1 chloride ion by the manganese porphyrin, as
we have described. [0236] 2. Then, ClO.sub.2 quickly reacts with
cyanide, forming chlorite and either cyanogen radical (by
2-electron pathway) or cyanate (by 1-electron pathway). [0237] 3.
The chlorite generated in Step 2 is recycled to Step 1. [0238] 4.
Gradually, the oxidation products of cyanide are hydrolyzed to give
carbon dioxide, oxalic acid, and 1-cyanoformamide.
[0239] Pathway Stoichiometry.
[0240] A variety of experimental parameters determine the
effectiveness of alkaline-chlorination-oxidation processes for any
particular cyanide treatment application. To deploy a new
technology that detoxifies cyanide would require a detailed
knowledge of reaction rates and side reactions at a range of
reagent concentrations and pH conditions.
[0241] The stoichiometry of chlorite and the cyanide oxidation
products may be calculated for both oxidation pathways simply by
combining the known balanced equations for ClO.sub.2 generation and
ClO.sub.2 utilization, treating ClO.sub.2 as an intermediate. Under
the conditions assessed in this work (5 .mu.M Mn(TM-2-PyP)
catalyst, 40 mM sodium chlorite (NaClO.sub.2), 40 mM NaCN, at pH
7.2 in 100 mM phosphate buffer), the partitioning between the two
cyanide oxidation pathways was roughly equal. These two pathways
are each combined with the ClO.sub.2 generation equation
illustrated in FIG. 16. Referring to this figure, first, 5 equiv
chlorite are oxidized to 4 equiv chlorine dioxide (ClO.sub.2) by
the porphyrin, generating 1 equiv chloride byproduct. ClO.sub.2
immediately oxidizes cyanide to cyanate or cyanogen, giving
chlorite (ClO.sub.2.sup.-) product which is recycled back to the
catalytic cycle. Cyanate and cyanogen are ultimately hydrolyzed to
carbon dioxide and oxalic acid, respectively. All of the C.sub.1
atoms from the initial chlorite sample are ultimately funneled into
the byproducts of the catalytic cycle, understood o be primarily
chloride ion.
[0242] Generation of ClO.sub.2.
[0243] The overall chemical equation described by Umile and Groves
for consumption of chlorite by the porphyrin catalyst is:
4H.sup.++5ClO.sup.-.fwdarw.4ClO.sub.2+Cl.sup.-+2H.sub.2O (3)
[0244] To simplify the preliminary calculations here, it is assumed
that this mechanism is still operative in the presence of cyanide.
However, the presence of cyanide was seen to speed the chlorite
depletion, suggesting that a different mechanism may be
operative.
[0245] Utilization of ClO.sub.2: Oxidation to Cyanogen
[0246] If chlorine dioxide reacts with cyanide to form cyanogen
radical, then the overall transformation is Equation (4.6):
4H++5ClO.sub.2.sup.-.fwdarw.4ClO.sub.2+Cl.sup.-+2H.sub.2O (4)
4ClO.sub.2+4CN.sup.-.fwdarw.4.CN+4ClO.sub.2.sup.- (5)
4H++ClO.sub.2.sup.-+4CN.sup.-.fwdarw.4.CN+Cl.sup.-+2H.sub.2O
(6)
[0247] Thus, if cyanide reacts with ClO.sub.2 through a
one-electron oxidation pathway, one chlorite is used to oxidize
four cyanide ions to four cyanogen radicals, creating one Cl.sup.-
byproduct. Notably, this reaction is pH-dependent, with the forward
reaction favored under acidic conditions.
[0248] Utilization of ClO.sub.2: Oxidation to Cyanate
[0249] Alternatively, cyanide can react with two equivalents of
ClO.sub.2 and two equivalents of hydroxide to form the cyanate
anion (OCN.sup.-), giving the overall transformation in (9):
4H++5ClO.sub.2-.fwdarw.4ClO.sub.2+Cl-+2H.sub.2O (7)
4ClO.sub.2+2CN-+4HO-.fwdarw.2OCN-+4ClO.sub.2-+2H.sub.2O (8)
ClO.sub.2.sup.-+2CN.sup.-.fwdarw.2OCN.sup.-+Cl.sup.- (9)
Thus, if cyanide reacts with ClO.sub.2 through this pathway, one
chlorite is used to oxidize two cyanide ions to two cyanate anions,
creating one chloride as a by-product. This reaction is not
pH-dependent.
[0250] Thus, by the cyanogen pathway, one equiv chlorite generates
two cyanogen (N--C--C--N) molecules and this reaction is favored
under acidic conditions. Alternatively, by the cyanate pathway, one
equiv chlorite generates two cyanate anions. This treatment
suggests that acidic conditions may favor the generation of
cyanogen, and that recycling allows one equivalent of chlorite to
oxidize 2-4 equivalents of cyanide.
[0251] The discrepancy between the ratios of cyanide oxidation
products (cyanate vs. cyanogen) observed for the control and
catalytic experiments herein may, for example, be explained by
porphyrin-catalyzed cyanide oxidation. Metal ions and metal
complexes including high-valent oxometalloporphyrins have been
found to be good oxidants for detoxifying cyanide. In this context,
the high-valent Mn.sup.V (TM-2-PyP) and Mn.sup.IV (TM-2-PyP) formed
turnover may be responsible for some of the observed cyanide
oxidation.
[0252] Materials and Methods.
[0253] Authentic ClO.sub.2 was prepared according to a previously
reported procedure. All other samples using catalysts and chlorite
were prepared from the materials described in that paper.
13-labeled KCN was obtained from Sigma-Aldrich and used as
received.
[0254] All .sup.13C NMR experiments were conducted on Bruker AVANCE
NMR instruments at 125 MHz. CN.sup.- and HCN can be difficult to
measure by NMR because they have a long relaxation time, but NMR
experiment settings were chosen to meet this challenge.
[0255] For the samples that contained 13-labeled cyanide as the
only carbon source, 32 scans were taken, and D1=60, P1=3. A control
spectrum of natural abundance cyanate was obtained by preparing 40
mM sodium cyanate in 10:90 H.sub.2O:D.sub.2O solution with 100 mM
phosphate buffer at pH 6.8. For this spectrum (FIG. 13), 800 scans
were taken, with D1=40, P1=5, and TD=131072. To calibrate chemical
shifts, the water-soluble calibration standard
4,4-dimethyl-4-silapentane-1-sulfonic acid (DSS), was used.
[0256] In order to further understand Equation (1), the reverse
reaction was performed. The reaction between 1:1 cyanate and
chlorite gave <1% yield of ClO.sub.2 in ten minutes. In
contrast, the reverse reaction between ClO.sub.2 and CN.sup.- to
form chlorite proceeded roughly to completion on the order of two
seconds, as shown in the titration in FIG. 12. Clearly, the
equilibrium rate constant K.sub.eq of Equation (1) is much greater
than 1.
[0257] Calculation of 1-Cyanoformamide Spectrum
[0258] The .sup.13C NMR results in this chapter necessitated a
reference spectrum for 1-cyanoformamide, which could not be found
in the literature. Therefore, the Gaussian 03 computational suite
was used to estimate the 1-cyanoformamide spectrum by DFT
calculation. The B3LYP hybrid functional was paired with the
6-311+G(2d,p) basis set, which has been found to be highly accurate
for small organic molecules. The subroutine GIAO (gauge-including
atomic orbital) was used calculate isotropic shielding values.
Chemical shifts were calculated to be 115.34 and 146.66, creating a
coupling constant of J.sub.CC=97.2 Hz and J.sub.CN=9.06 Hz for the
C--N pair.
[0259] The investigation of the effect of cyanide on the
MnPor/chlorite catalytic mechanism called into question whether
catalysis was responsible for the rapid consumption of chlorite.
Accordingly, experiments described herein have confirmed that
ClO.sub.2 is indeed generated catalytically from chlorite. This
confirmation has thus allowed investigating the effect of cyanide
on the MnPor/chlorite catalytic mechanism. These results have
potential industrial applications. A novel catalytic cycle for the
oxidation of aqueous cyanide has been developed. In this cycle, the
chlorite ion is oxidized by the water-soluble manganese porphyrin
catalyst tetra(N-methyl-2-pyridyl)porphyrinatomanganese(III)
(Mn.sup.III (TM-2-PyP)) to give an intermediate, the potent oxidant
chlorine dioxide. In this pathway, ClO.sub.2 quickly reacts with
cyanide, oxidizing it and in the process regenerating chlorite.
Thus, the chlorite starting material may be recycled, with each
chlorite ion oxidizing up to four equivalents of cyanide. The
cyanide oxidation products are ultimately hydrolyzed to two
products that are much less toxic: CO.sub.2 and oxalic acid. In
conclusion, this novel reactive pathway could form the basis for a
new cyanide detoxification process that could be utilized in
industry and the environment.
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[0334] The references cited throughout this application, are
incorporated for all purposes apparent herein and in the references
themselves as if each reference was fully set forth. For the sake
of presentation, specific ones of these references may be cited at
particular locations herein. A citation of a reference at a
particular location indicates a manner(s) in which the teachings of
the reference are incorporated. However, a citation of a reference
at a particular location does not limit the manner in which all of
the teachings of the cited reference are incorporated for all
purposes.
[0335] It is understood, therefore, that this invention is not
limited to the particular embodiments disclosed, but is intended to
cover all modifications which are within the spirit and scope of
the invention as defined by the appended claims; the drawings
and/or the above description.
* * * * *
References